Bi-Functionalized Polysiloxane Brush Copolymers

Abstract

The invention relates to a bi-functionalized polysiloxane brush copolymer comprising at least one hydroxyl-terminated polyalkyleneglycol side chain and at least one onium-functionalized side chain as defined herein, and a method for preparing the bi-functionalized polysiloxane brush copolymer, a curable composition comprising the bi-functionalized polysiloxane brush copolymer and its use.

Claims

1. A bi-functionalized polysiloxane brush copolymer, comprising: at least one hydroxyl-terminated polyalkyleneglycol side chain —[—S—B]; and at least one onium-functionalized side chain -[T-C], wherein: B represents hydroxyl-terminated polyalkyleneglycol side chain; S is a linker group wherein the moiety Si—C—C— of which said Si is a part of the polysiloxane backbone; C represents an onium-functionalized side chain; T is a linker group wherein the moiety of Si-heteroatom-C— of which said Si is a part of the polysiloxane backbone.

2. The bi-functionalized polysiloxane brush copolymer according to claim 1, wherein the polysiloxane backbone contains less than 500 ppm mol % of SiH moiety based on the total moles of the silicon atom which constitutes the polysiloxane backbone.

3. The bi-functionalized polysiloxane brush copolymer according to claim 1, wherein said copolymer has the number average molecular weight (Mn) of from 1000 to 200,000 g/mol.

4. The bi-functionalized polysiloxane brush copolymer according to claim 1, wherein said copolymer is represented by Formula (I) ##STR00015## wherein: Z is a covalent bond or selected from a polyoxyalkylene having a molecular weight of less than 10000 g/mol or a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom; each R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be the same or different and are independently selected from a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom, wherein R.sup.3, R.sup.4 and R.sup.5 may be independently selected in each unit n1, n2, n3, n4, and p; R.sup.11 is selected from a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom; R.sup.6 is selected from hydrogen or a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom; R.sup.7, R.sup.8, R.sup.9 and R.sup.10 may be the same or different and in each unit m they are independently selected from hydrogen or a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom; A is a heteroatom, or a heteroatom-containing group; W is selected from a linear, branched or cyclic hydrocarbon residue having 2 to 60 carbon atoms which may contain at least one heteroatom; Y is an onium cation; X is an anion selected from halide anions, pseudohalide anions, oxoanions, anions from organic acids or inorganic anions; n1 and n2 are an integer independently selected from 0 to 1000, with the proviso that not both of n1 and n2 are 0; n3 is an integer selected from 1 to 1000; n4 is an integer from 0 to 10; p is an integer from 0 to 1000; and m is an integer from 1 to 1500.

5. The bi-functionalized polysiloxane brush copolymer according to claim 4, wherein in Formula (I): Z is a covalent bond or selected from a C.sub.1-C.sub.20 alkylene group, a C.sub.6-C.sub.18 arylene group or a C.sub.6-C.sub.18 aralkylene group, which may contain at least one heteroatom; and/or R.sup.6 is selected from a C.sub.1-C.sub.12alkyl group, a C.sub.3-C.sub.10 cycloalkyl group, a C.sub.6-C.sub.18 aryl group or a C.sub.6-C.sub.18 aralkyl group, which may contain at least one heteroatom; and/or R.sup.11 is CR.sup.a.sub.2 where each R.sup.a may be the same or different and is independently selected from hydrogen, a C.sub.1-C.sub.12 alkyl group, a C.sub.3-C.sub.10 cycloalkyl group, a C.sub.6-C.sub.18 aryl group or a C.sub.6-C.sub.18 aralkyl group, which may contain at least one heteroatom.

6. The bi-functionalized polysiloxane brush copolymer according to claim 4, wherein in Formula (I): A is selected from O, S, NR.sup.12 or PR.sup.12, where R.sup.12 is selected from hydrogen, a C.sub.1-C.sub.8 alkyl group, a C.sub.3-C.sub.10 cycloalkyl group, a C.sub.6-C.sub.18 aryl group or a C.sub.6-C.sub.18 aralkyl group, which may contain at least one heteroatom selected from O, N, S, P, Si, Cl, Br or F; and/or W is selected from a linear, branched or cyclic hydrocarbon residue having 2 to 20 carbon atoms, which may contain at least one heteroatom selected from O, N, S, P, Si, Cl, Br or F; and/or Y is an onium cation represented as ER.sup.cR.sup.d, wherein E is a positively charged atom selected from the 16.sup.th group of the periodic table, or ER.sup.cR.sup.dR.sup.e wherein E is a positively charged atom selected from the 15.sup.th group of the periodic table, wherein R.sup.c, R.sup.d and R.sup.e may be the same or different and each is independently selected from hydrogen, a C.sub.1-C.sub.8 alkyl group, a C.sub.3-C.sub.10 cycloalkyl group, a C.sub.6-C.sub.18 aryl group or a C.sub.6-C.sub.18 aralkyl group, which may contain at least one heteroatom selected from O, N, S, Si, Cl, Br or F; and/or X is an anion selected from halide anions selected from Br.sup.−, I.sup.− or Cl.sup.−; pseudohalide anions selected from cyanide (CN.sup.−), azide (N.sub.3.sup.−), cyanate (OCN.sup.−), isocyanate (NCO.sup.−), thiocyanate (SCN.sup.−), or isothiocyanate (NCS.sup.−); oxoanions selected from nitrate, perchlorate, phosphate, sulfate, sulfite, or thiosulfate; anions from organic acids selected from acetate, formate, benzoate, or oxalate; or inorganic anions selected from Tf.sub.2N.sup.−, BF.sub.4.sup.−, SbF.sub.6.sup.− or PF.sub.6.sup.−.

7. The bi-functionalized polysiloxane brush copolymer according to claim 4, wherein in Formula (I) each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are independently selected from a C.sub.1-C.sub.12 alkyl group, a C.sub.3-C.sub.10 cycloalkyl group, a C.sub.6-C.sub.18 aryl group or a C.sub.6-C.sub.18 aralkyl group, which may contain at least one heteroatom.

8. The bi-functionalized polysiloxane brush copolymer according to claim 4, wherein in Formula (I) R.sup.7, R.sup.8 and R.sup.10 are hydrogen; and R.sup.9 is either a phenyl group or a C.sub.1-C.sub.8 alkyl group.

9. A method for preparing a bi-functionalized polysiloxane brush copolymer according to claim 1, comprising the steps of: a) reacting a hydroxyalkyl allyl ether having a primary or secondary alcohol group with a polyhydridosiloxane under catalysis of a transition metal catalyst of which the transition metal is selected from Groups 8 to 10 of the Periodic Table to provide a hydroxyl-functionalized polysiloxane prepolymer having Formula (II), ##STR00016## wherein: Z is a covalent bond or selected from a polyoxyalkylene having a molecular weight of less than 10000 g/mol or a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom; each R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be the same or different and are independently selected from a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom, wherein R.sup.3, R.sup.4 and R.sup.5 may be independently selected in each unit n1, n2, n4, and p; R.sup.11 is selected from a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom; R.sup.6 is selected from hydrogen or a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom; n1 and n2 are an integer independently selected from 0 to 1000, with the proviso that not both of n1 and n2 are 0; n4 is an integer from 1 to 1000; and p is an integer from 0 to 1000, said hydroxyalkyl allyl ether conforming to Formula (III), and ##STR00017## wherein: Z, R.sup.11 and R.sup.6 are the same as defined for Formula (II), said polyhydridosiloxane conforming to Formula (IV) ##STR00018## wherein: R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and p are the same as defined for Formula (II); and n is n1+n2+n4, wherein n1, n2 and n4 are the same as defined for Formula (II), b) in the presence of the obtained hydroxyl-functionalized polysiloxane prepolymer of Formula (II) and a catalyst, performing a ring-opening polymerization of at least one alkylene oxide monomer having Formula (V) to obtain a SiH-containing polysiloxane-g-polyalkenylglycol brush polymer of Formula (VI) ##STR00019## wherein: each R.sup.7, R.sup.8, R.sup.9 and R.sup.10 may be the same or different and are independently selected from hydrogen or a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom, ##STR00020## wherein: R.sup.1 to R.sup.11, Z, n1, n2, n4, p and m are the same as defined for Formulas (II) to (V), c) reacting the obtained SiH-containing polysiloxane-g-polyalkenylglycol brush polymer of Formula (VI), at least one heterocyclic compound, and at least one compound of Formula (VIII) in the presence of at least one metal catalyst to obtain a polymer of Formula (VII) ##STR00021## wherein: R.sup.1 to R.sup.11, Z, n1, n2, p and m are the same as defined for the Formula (VI); A is a heteroatom, or a heteroatom-containing group; W is selected from a linear, branched or cyclic hydrocarbon residue having 2 to 60 carbon atoms which may contain at least one heteroatom; X is selected from halogen atoms, pseudohalogen groups, polyatomic groups resulting from the replacement of a proton in oxoacids, polyatomic groups resulting from the replacement of a proton in organic acids; n3 is from 1 to 1000; n4 is an integer from 0 to 10, ##STR00022## wherein: X is the same as defined for the Formula (VII); and R.sup.b is selected from the group consisting of hydrogen or a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom, and d) nucleophilic substitution of the X on the polymer of Formula (VII) by a nucleophile containing at least one atom selected from the 15.sup.th or 16.sup.th group of the periodic table, optionally in the absence of a catalyst.

10. The method according to claim 9, wherein the catalyst of step b) is an alkoxylation catalyst selected from the group consisting of alkali metal hydroxides, alkali earth metal hydroxides, alkali metal alkoxides, alkali earth metal alkoxides, and double metal cyanide complex.

11. The method according to claim 9, wherein the catalyst of step c) is a platinum catalyst or palladium catalyst; and/or the heterocyclic compound used in step c) is selected from the group consisting of ethylene oxide, 1,2-propylene oxide, tetrahydrofuran, 2-Methyltetrahydrofuran, oxetane, oxetene, tetrahydropyrane, oxepane, 1,4-dioxane, crown ethers, epichlorhydrin, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentylene oxide, isopentylene oxide, 1,2-hexylene oxide, 1,2-heptylene oxide, styrene oxide, cyclohexene oxide, methylglycidyl ether, ethylglycidyl ether, allylglycidyl ether, phenylglycidyl ether, butadiene monoxide, isoprene monoxide, tolylglycidyl ether, cyclohexene oxide, cyclooctanee epoxide, cyclododecane epoxide, (+)-cis-limonene oxide, (+)-cis, trans-limonene oxide and (−)-cis, trans-limonene oxide, lactones, dilactones, lactams, lactides, thiolactones, thiolane, piperidine, pyrroline, pyrrolidine, aziridine, azirine, oxirene, thiirane, thiirene, phosphirane, phosphirene, azetidine, azete, thietane and thiete, and ε-caprolactones.

12. The method according to claim 9, wherein the nucleophile used in step d) is selected from the group consisting of amines, phosphines, arsanes, ethers, alcohols, thiols, sulfides, and selenium-containing molecules.

13. A curable composition comprising at least one bi-functionalized polysiloxane brush copolymer according to claim 1.

14. A curable adhesive or a sealant or a coating composition comprising at least one bi-functionalized polysiloxane brush copolymer according to claim 1.

15. The curable adhesive or a sealant or a coating composition according to claim 14 wherein the bi-functionalized polysiloxane brush copolymer imparts antimicrobial properties against at least one of mold, yeast, fungus, gram-positive bacteria or gram-negative bacteria.

Description

EXAMPLES

Example 1: Preparation of 1-(allyloxy)propan-2-ol

[0178] ##STR00009##

[0179] In a 1 L autoclave equipped with dosage system, 637.5 g (10.98 mol) of allyl alcohol were placed. Under argon flow, Na (2.9% mol) was added into the vessel. The mixture was stirred at room temperature until the gas evolution ceased. Then the autoclave was closed and heated until 110° C. In the next step propylene oxide (PO) was dosed (520 ml, dosage rate 1.25 g/min). After the completion of the addition of PO it was allowed to cool to room temperature and the reaction mixture was stirred overnight. A yellow transparent mixture was obtained. The mixture was neutralized using HCl (solution 37% in water) and dried with Na.sub.2SO.sub.4. The mixture was filtrated trough celite and distilled under vacuum (100 mbar, 85-95° C.). The product was obtained with good yield (70-75%) and the structure was confirmed by NMR spectroscopy and mass spectrometry.

Example 2: Preparation of Poly(3-(2-hydroxypropoxy)propyl)methylsiloxane-co-polyhydridomethyl-co-polydimethylsiloxane

[0180] ##STR00010##

A 500 ml three neck round bottomed flask was degassed under high vacuum (1.sup.−3 mbar) and flushed with argon. Then, 120 μL of Karstedt (2% of Pt in the catalyst, 0.1% mol in the mixture) and toluene (200 ml, dried over molecular sieves) were added into the flask under argon atmosphere and stirred at room temperature (20° C.) for a couple of minutes. Then 1-(allyloxy)propan-2-ol (from Example 1; 5.73 ml) was added into the system. (25-35% Methylhydrosiloxane)-dimethylsiloxane copolymer (20.4 mL, Mn 3800 g/mol) were added dropwise. The mixture was stirred and refluxed (oil bath temperature: 120° C.) under inert atmosphere (Ar) until 50% conversion of the SiH groups was achieved (the reaction was followed by .sup.1H-NMR). The mixture (when necessary) was decolorized by adding activated carbon and an excess of pentane and stirred for 16 h at room temperature. The crude was filtrated trough celite, and the solvents and volatiles were evaporated under vacuum. The obtained product (yield 84%) was a colorless, transparent viscous liquid. The molecular weight and structure of the product was confirmed by GPC (Mn=7891 g/mol, PDI 4.532) and NMR spectroscopy.

Example 3: Preparation of Poly(3-(2-hydroxypropoxy)propyl)methylsiloxane-co-polyhydridomethyl-co-polydimethylsiloxane

[0181] ##STR00011##

[0182] A 100 ml three neck round bottomed flask was degassed under high vacuum (1.sup.−3 mbar) and flushed with argon. Then, 60 mg of Platinum supported on charcoal (10% of Pt in the catalyst, 0.5% mol in the mixture compared to siloxane starting material) and toluene (40 ml, dried over molecular sieves) were added into the flask under argon atmosphere and stirred at room temperature (20° C.) for a couple of minutes. Then 1-(allyloxy)propan-2-ol (the product from Example 1; 1.42 mL) was added into the system. (25-35% Methylhydrosiloxane)-dimethylsiloxane copolymer (5.1 mL, Mn 3800 g/mol) were added dropwise. The mixture was stirred (oil bath temperature: 100° C.) under inert atmosphere (Ar) until 50% conversion of the SiH groups was achieved (the reaction was followed by .sup.1H-NMR). The mixture (when necessary) was decolorized by adding activated carbon and an excess of pentane and stirred for 16 h at room temperature. The crude was filtrated trough celite, and the solvents and volatiles were evaporated under vacuum. The obtained product (yield 75%) was a colorless, transparent viscous liquid. The molecular weight and structure of the product was confirmed by GPC (Mn=5929 g/mol, PDI 2.645) and NMR spectroscopy.

Example 4: Preparation of Polydimethylsiloxane-graft-poly(propyleneoxide)-co-polyhydridomethylsiloxane

[0183] ##STR00012##

5.0 g of (3-(2-hydroxypropoxy)propyl)methylsiloxane-co-polyhydridomethyl-co-polydimethylsiloxane (from Example 2, Mn=7891 g/mol, PDI 4.532) were charged together with 0.015 g of the DMC catalyst (170 ppm based on the amount of the copolymer) and 20.0 g heptane in a 100 mL-stirring Autoclave. The reaction mixture was stirred at room temperature with constant stirring at 350 rpm for several minutes under vacuum (0.001 bar) and argon atmosphere (1 bar). Then the reaction temperature was increased at 110° C. After reaching this temperature, 3.5 mL propylene oxide (PO) were added to the reaction mixture and stirred constantly at 350 rpm. After filtration (when necessary) the solvent and traces of unreacted monomer were removed under vacuum (0.001 bar) for three hours. The yield of the product was found to be 89%. The product is milky, colorless, viscos liquid. The molecular weight and structure of the product was confirmed by GPC (Mn=8500 g/mol, PDI 3.722) and NMR spectroscopy.

Example 5: Preparation of Polydimethylsiloxane-co-poly(3-(2-hydroxypropoxy)propyl)methylsiloxane-co-poly(3-(4-bromobutoxy))methylsiloxane

[0184] ##STR00013##

[0185] A 100 ml three neck round bottomed flask was degassed under high vacuum (1.sup.−3 mbar) and flushed with argon. Poly((hydroxyl)-polypropylenglycol)methylsiloxane-co-polyhydridomethyl-co-polydimethylsiloxane (6.5 g, Mn 6411 g/mol, PDI 4.484) was added. Then THF (20 mL, dried over molecular sieves) and allyl bromide (0.52 mL, 97%) were added into the flask under argon atmosphere and stirred at room temperature (20° C.) for a couple of minutes. Then, PdCl.sub.2 (2 mg, 1.6 mol-% in the mixture) added into the system. The mixture was stirred (oil bath temperature: 50° C.) under inert atmosphere (Ar) until complete conversion of the SiH groups was achieved (the reaction was followed by .sup.1H-NMR). The mixture (when necessary) was decolorized by adding activated carbon and an excess of pentane and stirred for 16 h at room temperature. The crude was filtrated trough celite, and the solvents and volatiles were evaporated under vacuum. The obtained product (yield >95%) was a yellow, milky, viscous liquid. The molecular weight and structure of the product was confirmed by GPC (Mn=6300 g/mol, PDI 3.434) and NMR spectroscopy. The elements were detected by EA.

Example 6: Preparation of Polydimethylsiloxane-graft-poly(propylene oxide)-co-poly(3-(4(methylsiloxane)butoxy)pyridinium Bromide

[0186] ##STR00014##

[0187] A 100 ml three neck round bottomed flask was degassed under high vacuum (1.sup.−3 mbar) and flushed with argon. Poly((hydroxyl)-polypropylenglycol)methylsiloxane-co-poly(3-(4-bromobutoxy))methylsiloxane-co-polydimethylsiloxane (from Example 5, 7.3 g, Mn=6300 g/mol, PDI 3.434) was added. Then toluene (15 mL, dried over molecular sieves) and ethanol (15 mL, dried over molecular sieves) were added into the flask under argon atmosphere and stirred at room temperature (20° C.) for a couple of minutes. Then pyridine (0.5 mL, 99%) was added into the system. The mixture was stirred (oil bath temperature: 75° C.) under inert atmosphere (Ar) until complete quaternization was achieved (the reaction was followed by .sup.1H-NMR). The solvents and volatiles were evaporated under vacuum. The obtained product (yield 84%) was a grey, milky, high viscous liquid. The molecular weight and structure of the product was confirmed by GPC (Mn=5167 g/mol, PDI 5.656) NMR spectroscopy. The elements were detected by EA.

[0188] Methods

[0189] NMR-Spectroscopy: All NMR measurements were done on a Bruker 300 MHz, 400 MHz and 600 MHz instrument with deuterated DMSO and methanol as solvent. All the samples were measured at room temperature (297 K). The chemical shifts are given in ppm. The calibration of the chemical shifts in 1H spectra was carried out by using the shifts of the deuterated solvents (DMSO-d6, δ H 2.49, 39.7; CD3OD, δ H 3.31, 49.0).

[0190] GPC: The molecular weights given in the present text refer to number average molecular weights (Mn), unless otherwise stipulated. All molecular weight data refer to values obtained by gel permeation chromatography (GPC) carried out using HP1090 II Chromatography with DAD detector (HEWLETT PACKARD) at 40° C. Tetrahydrofuran (THF) was used as an eluent. THF was passed through three PSS SDV gel columns with molecular weight ranges of 102, 103 and 104 g.Math.mol.sup.−1 with a flow rate of 0.9 ml.Math.min.sup.−1. The calibration of the device was carried out using polystyrene standards.

[0191] Elemental Analysis (EA): Elemental analyses were recorded with a Flash EA 1112 analyzer by Thermo Quest or with a C/H/N/S-micro analyzer TruSpec-932 by Leco. The determination of halogens was done with a potentiometric titration (analytical titration TIM 580 und TIM 870). Detection of silicon was done via atomic absorption spectrometry with Perkin-Elmer AAnalyst 300.