WO2010024661A2 - Lipophilic ammonium borate salts - Google Patents
Lipophilic ammonium borate salts Download PDFInfo
- Publication number
- WO2010024661A2 WO2010024661A2 PCT/MY2009/000126 MY2009000126W WO2010024661A2 WO 2010024661 A2 WO2010024661 A2 WO 2010024661A2 MY 2009000126 W MY2009000126 W MY 2009000126W WO 2010024661 A2 WO2010024661 A2 WO 2010024661A2
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- WIPO (PCT)
- Prior art keywords
- lipophilic
- ammonium
- immobilized
- borate salt
- ammonium borate
- Prior art date
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- NTBYNMBEYCCFPS-UHFFFAOYSA-N azane boric acid Chemical class N.N.N.OB(O)O NTBYNMBEYCCFPS-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000012528 membrane Substances 0.000 claims abstract description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 11
- 125000000129 anionic group Chemical group 0.000 claims abstract description 11
- 125000002091 cationic group Chemical group 0.000 claims abstract description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 230000002209 hydrophobic effect Effects 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- URSLCTBXQMKCFE-UHFFFAOYSA-N dihydrogenborate Chemical class OB(O)[O-] URSLCTBXQMKCFE-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 11
- -1 borate ions Chemical class 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 8
- 239000000178 monomer Substances 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract 1
- OGFYIDCVDSATDC-UHFFFAOYSA-N silver silver Chemical compound [Ag].[Ag] OGFYIDCVDSATDC-UHFFFAOYSA-N 0.000 abstract 1
- 150000001768 cations Chemical class 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 150000001642 boronic acid derivatives Chemical class 0.000 description 3
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 3
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229920001600 hydrophobic polymer Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- BNZLTPCWOLWBNJ-UHFFFAOYSA-M Br[Mg] Chemical compound Br[Mg] BNZLTPCWOLWBNJ-UHFFFAOYSA-M 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- DBDNZCBRIPTLJF-UHFFFAOYSA-N boron(1-) monohydride Chemical compound [BH-] DBDNZCBRIPTLJF-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical class [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
- G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
Definitions
- the present invention relates to the preparation of lipophilic ammonium borate salts. More particularly, the present invention relates to the preparation of immobilized highly lipophilic ammonium borate salts for creating cationic and anionic sites in hydrophobic polymer membranes wherein the salt is covalently bonded to the polymer backbone.
- the conventional detection of various types of chemical uses electrochemical sensors designed for determining a particular chemical's concentration and its activity.
- the electrochemical sensors generally have sensing membranes specifically formulated for measuring the chemical species of interest.
- Lipophilic borate salts have been used to create anionic sites in chemical sensor membranes. This allows positively charged species such as metal cations to be transported across the membrane. Likewise, lipophilic tetraalkyl ammonium salts (usually chloride salts) have been employed to create positively charged sites in hydrophobic membrane in order to allow passage of anions.
- ammonium borate salts can create at the same time both cationic and anionic sites in lipophilic membranes. Moreover, equal number of the opposite charges can be created by the lipophilic ammonium borate salts.
- the present invention provides preparation of lipophilic ammonium borate salts, wherein the salts are covalently bonded to hydrophobic organic membranes and thus immobilized to the polymer backbone.
- the immobilized ammonium borate salts are used to create sufficient and equal number of positively and negatively charged species in lipophilic membrane.
- the charge-balanced doped lipophilic membrane created by the immobilized ammonium borate salt when coupled to hydrophilic membrane containing internal chloride electrolyte covering silver-silver chloride electrode, functions as liquid-free reference electrode suitable for field deployment on integrated multi-sensors.
- United States patent No. 5,473,036 discloses formation of bromomagnesium tetrakis(fluorophenyl) borate reactible intermediate by reacting at least four equivalents of fluorophenyl magnesium bromide with every one equivalent of boron trifluoride in ether solvent. This reactible intermediate can then be reacted with a salt containing a suitable cation, such as substituted ammonium, trityl or onium to form the desired combination of weakly coordinating boron anion and activating cation.
- a salt containing a suitable cation such as substituted ammonium, trityl or onium
- United States patent publication No. US 2006/0065527 A1 discloses a polymeric reference electrode which contains a polymeric membrane comprising a polyacrylate backbone and pendant lipophilic plasticizing groups that provide the polymer with a sufficiently low glass transition temperature (T 9 ) to mimic the characteristics of a highly plasticized thermoplastic membrane.
- United States patent No. 4,379,041 discloses a polymeric membrane selective to calcium (II) ions formed by solid film of plastic material which contains a complex of macrocyclic polyetherdiamides and a lipophilic organic anion, preferably with tetraphenylborate or tetra(p-chlorophenyl)borate anion.
- the present invention discloses the synthesis of immobilized lipophilic ammonium borate salts 1, 2 and 3 from tetra-substituted borate anion and immobilized lipophilic ammonium cation having long-chain alkyl or fluorinated substituents.
- the said tetra-substituted borate anion is sodium tetrakis(3,5- trifluoromethylphenyl) borate; while the said immobilized lipophilic ammonium cation having long-chain alkyl or fluorinated substituents is ammonium chloride i, ii and iii.
- the immobilized lipophilic ammonium borate salt 1 has the formula:
- the immobilized lipophilic ammonium borate salt 2 has the formula:
- the immobilized lipophilic ammonium borate salt 3 has the formula:
- the immobilized lipophilic ammonium borate salt 1, 2 or 3 is used as immobilized lipophilic agent in hydrophobic chemical sensor membrane and as lipophilic ionic components in polymeric reference electrode.
- the said ammonium borate salt 1, 2 or 3 creates cationic and anionic sites in hydrophobic chemical sensor membrane.
- the said chemical sensor membrane comprises acrylic, urethane, polymer, lipophilic ammonium borate salt 1 , 2 or 3 and combination thereof.
- the present invention relates to preparation of highly lipophilic ammonium borate salts. More particularly, the present invention relates to preparation of immobilized highly lipophilic ammonium borate salts for creating cationic and anionic sites in hydrophobic polymer membranes wherein the salt contains moiety that covalently bond to the membrane monomer and thus immobilized to the polymer backbone. This gives significant advantage in terms of the membrane lifetime since the salt is prevented from leaching to the fluidic analyte. Moreover, the formation of both cationic and anionic lipophilic sites in hydrophobic membrane can be used to create balanced total number of positive and negative charges in the hydrophobic membrane.
- Covalent bonding between the ammonium borate salt and the membrane monomer would result in immobilization of the salt to the polymer backbone.
- Polymerization can take place under UV exposure, and both monomer and ammonium borate salts should contain unsaturated carbon or carbon double bond.
- Photo-initiator and crosslinker are usually added to produce membrane with desirable sensing capability.
- Polyvinyl chloride (PVC), polyurethane, urethane, silicone rubber and acrylic membranes have been widely used in making chemical sensors.
- acrylates are of special interest due to its low transition temperature (T 9 ). This implies that acrylic membrane can be self- plasticized and can be used as sensing membrane without plasticizer additives. Consequently, acrylate moiety can be introduced to ammonium borate salts so that it can polymerize with acrylate monomer.
- T 9 transition temperature
- the monomer acts as natural solvent that readily dissolves lipophilic ammonium borates.
- preparation of immobilized lipophilic ammonium borates 1, 2 and 3 are described. The immobilized salts are used to create sufficient and equal number of positively and negatively charged sites in hydrophobic membranes.
- the charge-balanced lipophilic membrane When coupled to hydrophilic membrane containing chloride internal electrolyte, covering the surface of silver-silver chloride electrode, the charge-balanced lipophilic membrane can be used to make planar liquid-free reference electrode.
- the hydrophobic membrane in contact with silver-silver chloride electrode can function as a planar lipophilic reference electrode that is suitable for integration with chemical multi-sensors and deployment in harsh field environment.
- Lipophilic anionic sites are created in hydrophobic sensing membrane using bulky tetra-substituted borate anions.
- fluorinated tetraphenyl borate salts are employed.
- Bulky borate salts exhibits tetrahedral crystal structure.
- the negatively charged boron center is physically shielded by the bulky phenyl ring substituent, causing loose interaction between the anion and its cation pair such as sodium or potassium ions. This in turn allows passage of cations across the anionic doped hydrophobic membrane without showing apparent selectivity or preference on any particular cation.
- cationic sites in polymeric membrane are introduced using long-chain substituted tetra-alkyl or fluorinated ammonium salts (usually chlorides).
- the straight long chain alkyl or fluorinated substituents increase lipophilicity of the ammonium cation and improve its solubility in lipophilic polymeric membrane.
- Lipophilic ammonium ion is also sterically shielded by the long-chain or fluorinated substituent.
- the positively charged nitrogen center is loosely interacted with its ion pair (usually chloride). This makes the lipophilic ammonium salts suitable to create cationic sites and to allow transport of negatively charged species, without apparent preference.
- immobilized ammonium borate is used to create equal number of positive and negative lipophilic sites in hydrophobic sensing membranes.
- Equal number of lipophilic cationic and anionic sites can be created by doping polymeric membrane with equivalent moles of lipophilic ammonium halide salt (usually chloride) and sodium or potassium borate.
- Lipophilic ammonium borate salts 1 , 2, and 3 are prepared in the following reaction, starting from respective quaternary ammonium chloride and sodium tetrakis(3,5-trifluoromethylphenyl)borate;
- Chemical reagents were used as received without further purifications.
- Sodium tetrakis(3,5-trifluoromethylphenyl)borate was purchased from Fluka. Solvents were procured from Aldrich Chemical Company and were dried and purified by distillation following literature procedures. Lipophilic ammonium chlorides were freshly prepared before use.
- Lipophilic ammonium borate 2 was prepared from 1.5 mmol of sodium tetrakis(3,5-trifluoromethylphenyl)borate and 1.5 mmol of freshly prepared ammonium chloride ii. The same procedure as described in Example 1 was followed to afford 70% yield of lipophilic ammonium borate salt 2.
- lipophilic ammonium borate 3 was prepared from 1.5 mmol of sodium tetrakis(3,5-trifluoromethylphenyl)borate and 1.5 mmol of freshly prepared ammonium chloride iii. The same procedure as described in Example 1 was followed to afford 75% yield of lipophilic ammonium borate salt 3.
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- Organic Chemistry (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The present invention relates to preparation of immobilized lipophilic ammonium borate salts, wherein the salt can form covalent bond with the monomer of sensing membrane and thus immobilized to the matrix backbone. The sterically shielded ammonium and borate ions create equal number of lipophilic cationic and anionic sites that are loosely bound and when in contact with silver-silver electrode can function as planar reference electrode.
Description
LIPOPHILIC AMMONIUM BORATE SALTS
Field of the Invention
The present invention relates to the preparation of lipophilic ammonium borate salts. More particularly, the present invention relates to the preparation of immobilized highly lipophilic ammonium borate salts for creating cationic and anionic sites in hydrophobic polymer membranes wherein the salt is covalently bonded to the polymer backbone.
Background of the Invention
The conventional detection of various types of chemical uses electrochemical sensors designed for determining a particular chemical's concentration and its activity. The electrochemical sensors generally have sensing membranes specifically formulated for measuring the chemical species of interest.
Lipophilic borate salts have been used to create anionic sites in chemical sensor membranes. This allows positively charged species such as metal cations to be transported across the membrane. Likewise, lipophilic tetraalkyl ammonium salts (usually chloride salts) have been employed to create positively charged sites in hydrophobic membrane in order to allow passage of anions.
Based on the same principle, ammonium borate salts can create at the same time both cationic and anionic sites in lipophilic membranes. Moreover, equal number of the opposite charges can be created by the lipophilic ammonium borate salts.
The present invention provides preparation of lipophilic ammonium borate salts, wherein the salts are covalently bonded to hydrophobic organic membranes and thus immobilized to the polymer backbone. The immobilized ammonium borate salts are used to create sufficient and equal number of
positively and negatively charged species in lipophilic membrane. The charge-balanced doped lipophilic membrane created by the immobilized ammonium borate salt, when coupled to hydrophilic membrane containing internal chloride electrolyte covering silver-silver chloride electrode, functions as liquid-free reference electrode suitable for field deployment on integrated multi-sensors.
United States patent No. 5,473,036 discloses formation of bromomagnesium tetrakis(fluorophenyl) borate reactible intermediate by reacting at least four equivalents of fluorophenyl magnesium bromide with every one equivalent of boron trifluoride in ether solvent. This reactible intermediate can then be reacted with a salt containing a suitable cation, such as substituted ammonium, trityl or onium to form the desired combination of weakly coordinating boron anion and activating cation.
United States patent publication No. US 2006/0065527 A1 discloses a polymeric reference electrode which contains a polymeric membrane comprising a polyacrylate backbone and pendant lipophilic plasticizing groups that provide the polymer with a sufficiently low glass transition temperature (T9) to mimic the characteristics of a highly plasticized thermoplastic membrane.
United States patent No. 4,379,041 discloses a polymeric membrane selective to calcium (II) ions formed by solid film of plastic material which contains a complex of macrocyclic polyetherdiamides and a lipophilic organic anion, preferably with tetraphenylborate or tetra(p-chlorophenyl)borate anion.
Summary of the Invention
The present invention discloses the synthesis of immobilized lipophilic ammonium borate salts 1, 2 and 3 from tetra-substituted borate anion and immobilized lipophilic ammonium cation having long-chain alkyl or fluorinated substituents. The said tetra-substituted borate anion is sodium tetrakis(3,5-
trifluoromethylphenyl) borate; while the said immobilized lipophilic ammonium cation having long-chain alkyl or fluorinated substituents is ammonium chloride i, ii and iii.
The immobilized lipophilic ammonium borate salt 1 has the formula:
The immobilized lipophilic ammonium borate salt 2 has the formula:
The immobilized lipophilic ammonium borate salt 3 has the formula:
The immobilized lipophilic ammonium borate salt 1, 2 or 3 is used as immobilized lipophilic agent in hydrophobic chemical sensor membrane and as lipophilic ionic components in polymeric reference electrode. The said ammonium borate salt 1, 2 or 3 creates cationic and anionic sites in hydrophobic chemical sensor membrane. The said chemical sensor
membrane comprises acrylic, urethane, polymer, lipophilic ammonium borate salt 1 , 2 or 3 and combination thereof.
Detailed Description of the Invention The present invention relates to preparation of highly lipophilic ammonium borate salts. More particularly, the present invention relates to preparation of immobilized highly lipophilic ammonium borate salts for creating cationic and anionic sites in hydrophobic polymer membranes wherein the salt contains moiety that covalently bond to the membrane monomer and thus immobilized to the polymer backbone. This gives significant advantage in terms of the membrane lifetime since the salt is prevented from leaching to the fluidic analyte. Moreover, the formation of both cationic and anionic lipophilic sites in hydrophobic membrane can be used to create balanced total number of positive and negative charges in the hydrophobic membrane.
Covalent bonding between the ammonium borate salt and the membrane monomer would result in immobilization of the salt to the polymer backbone. Polymerization can take place under UV exposure, and both monomer and ammonium borate salts should contain unsaturated carbon or carbon double bond. Photo-initiator and crosslinker are usually added to produce membrane with desirable sensing capability.
Polyvinyl chloride (PVC), polyurethane, urethane, silicone rubber and acrylic membranes have been widely used in making chemical sensors. Among these materials, acrylates are of special interest due to its low transition temperature (T9). This implies that acrylic membrane can be self- plasticized and can be used as sensing membrane without plasticizer additives. Consequently, acrylate moiety can be introduced to ammonium borate salts so that it can polymerize with acrylate monomer. Another advantage is the monomer acts as natural solvent that readily dissolves lipophilic ammonium borates.
In this invention preparation of immobilized lipophilic ammonium borates 1, 2 and 3 are described. The immobilized salts are used to create sufficient and equal number of positively and negatively charged sites in hydrophobic membranes. When coupled to hydrophilic membrane containing chloride internal electrolyte, covering the surface of silver-silver chloride electrode, the charge-balanced lipophilic membrane can be used to make planar liquid-free reference electrode. The hydrophobic membrane in contact with silver-silver chloride electrode can function as a planar lipophilic reference electrode that is suitable for integration with chemical multi-sensors and deployment in harsh field environment.
1 : R1=R2=R3= (CH2)10CH3
2: R1=R2= (CH2)10CH3; R3= CH2(CF2)7CF3
3: R1 =R2=R3= (CH2)6CH3
Lipophilic anionic sites are created in hydrophobic sensing membrane using bulky tetra-substituted borate anions. Usually fluorinated tetraphenyl borate salts are employed. Bulky borate salts exhibits tetrahedral crystal structure. The negatively charged boron center is physically shielded by the bulky phenyl ring substituent, causing loose interaction between the anion and its cation pair such as sodium or potassium ions. This in turn allows passage of cations across the anionic doped hydrophobic membrane without showing apparent selectivity or preference on any particular cation.
Likewise, cationic sites in polymeric membrane are introduced using long-chain substituted tetra-alkyl or fluorinated ammonium salts (usually chlorides). The straight long chain alkyl or fluorinated substituents increase lipophilicity of the ammonium cation and improve its solubility in lipophilic
polymeric membrane. Lipophilic ammonium ion is also sterically shielded by the long-chain or fluorinated substituent. The positively charged nitrogen center is loosely interacted with its ion pair (usually chloride). This makes the lipophilic ammonium salts suitable to create cationic sites and to allow transport of negatively charged species, without apparent preference.
In this invention immobilized ammonium borate is used to create equal number of positive and negative lipophilic sites in hydrophobic sensing membranes. Equal number of lipophilic cationic and anionic sites can be created by doping polymeric membrane with equivalent moles of lipophilic ammonium halide salt (usually chloride) and sodium or potassium borate.
Lipophilic ammonium borate salts 1 , 2, and 3 are prepared in the following reaction, starting from respective quaternary ammonium chloride and sodium tetrakis(3,5-trifluoromethylphenyl)borate;
)7CF3
1: R1=R2=R3= (CH2)ioCH3
2: R1=R2= (CH2)10CH3; R3= CH2(CF2)7CF3
NaCI
3: R1=R2=R3= (CH2)6CH3
Detailed preparation procedures are provided in the following examples. Chemical reagents were used as received without further purifications. Sodium tetrakis(3,5-trifluoromethylphenyl)borate was purchased from Fluka. Solvents were procured from Aldrich Chemical Company and were dried and purified by distillation following literature procedures. Lipophilic ammonium chlorides were freshly prepared before use.
EXAMPLE 1 Preparation of Immobilized Lipophilic Ammonium Borate Salt 1 Dry three-neck round-bottom flask (50-mL) containing 1.5 mmol of ammonium chloride i in 20 mL of freshly distilled dichloromethane was purged with continuous flow of argon. To the stirred solution of i, 1.5 mmol of sodium tetrakis(3,5-trifluoromethylphenyl)borate in 15 mL of anhydrous acetone was added drop-wise through addition funnel. Stirring at room temperature was continued for 20 hours, before the solution was filtered through funnel to separate the sodium chloride precipitate. The solvent was removed by distillation through Vigreaux column and the residue was purified through silica gel column chromatography by successive elutions with hexanes, ethyl acetate and methanol to give 71% yield of lipophilic ammonium borate salt 1.
Lipophilic ammonium borate 2 was prepared from 1.5 mmol of sodium tetrakis(3,5-trifluoromethylphenyl)borate and 1.5 mmol of freshly prepared ammonium chloride ii. The same procedure as described in Example 1 was followed to afford 70% yield of lipophilic ammonium borate salt 2.
EXAMPLE 3 Preparation of Immobilized Lipophilic Ammonium Borate Salt 3
Likewise, lipophilic ammonium borate 3 was prepared from 1.5 mmol of sodium tetrakis(3,5-trifluoromethylphenyl)borate and 1.5 mmol of freshly prepared ammonium chloride iii. The same procedure as described in Example 1 was followed to afford 75% yield of lipophilic ammonium borate salt 3.
Claims
1. A method of preparing ammonium borate salt comprising the synthesis of immobilized lipophilic ammonium borate salt 1 from tetra- substituted borate anion and immobilized lipophilic ammonium cation having long-chain alkyl or fluorinated substituents.
2. A method of preparing ammonium borate salt comprising the synthesis of immobilized lipophilic ammonium borate salt 2 from tetra- substituted borate anion and immobilized lipophilic ammonium cation having long-chain alkyl or fluorinated substituents.
3. A method of preparing ammonium borate salt comprising the synthesis of immobilized lipophilic ammonium borate salt 3 from tetra- substituted borate anion and immobilized lipophilic ammonium cation having long-chain alkyl or fluorinated substituents.
4. The method of preparing ammonium borate salt according to claim 1 wherein said immobilized lipophilic ammonium borate salt 1 has the formula:
5. The method of preparing ammonium borate salt according to claim 2 wherein said immobilized lipophilic ammonium borate salt 2 has the formula: 
6. The method of preparing ammonium borate salt according to claim 3 wherein said immobilized lipophilic ammonium borate salt 3 has the formula:
7. The method of preparing ammonium borate salt according to any preceding claim wherein said tetra-substituted borate anion is sodium tetrakis(3,5-trifluoromethylphenyl) borate.
8. The method of preparing ammonium borate salt according to any preceding claim wherein said immobilized lipophilic ammonium cation having straight long-chain alkyl or fluorinated substituent is ammonium chloride i.
9. The method of preparing ammonium borate salt according to any preceding claim wherein said immobilized lipophilic ammonium cation having straight long-chain alkyl or fluorinated substituent is ammonium chloride ii.
10. The method of preparing ammonium borate salt according to any preceding claim wherein said immobilized lipophilic ammonium cation having straight long-chain alkyl or fluorinated substituent is ammonium chloride iii.
11. The use of immobilized lipophilic ammonium borate salt 1 , 2 or 3 according to any preceding claim as immobilized lipophilic agent in hydrophobic chemical sensor membrane.
12. The use of immobilized lipophilic ammonium borate salt 1, 2 or 3 according to any preceding claim for creating cationic and anionic sites in hydrophobic chemical sensor membrane.
13. The use of immobilized lipophilic ammonium borate salt 1 , 2 or 3 according to any preceding claim as lipophilic ionic components in polymeric reference electrode.
14. The chemical sensor membrane according to claim 11 further comprises acrylic, urethane, polymer, lipophilic ammonium borate salt 1, 2 or 3 and combination thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| MYPI20083262 | 2008-08-25 | ||
| MYPI20083262A MY158538A (en) | 2008-08-25 | 2008-08-25 | Lipophilic ammonium borate salts |
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| Publication Number | Publication Date |
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| WO2010024661A2 true WO2010024661A2 (en) | 2010-03-04 |
| WO2010024661A3 WO2010024661A3 (en) | 2010-06-24 |
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| PCT/MY2009/000126 WO2010024661A2 (en) | 2008-08-25 | 2009-08-21 | Lipophilic ammonium borate salts |
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| MY (1) | MY158538A (en) |
| WO (1) | WO2010024661A2 (en) |
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| CN108559134B (en) * | 2018-04-28 | 2020-04-24 | 陕西师范大学 | BaB8O11(OH)4nanosheet/SiO2Composite flame retardant and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004039761A1 (en) * | 2002-10-31 | 2004-05-13 | Honeywell Specialty Chemicals Seelze Gmbh | Direct process for the manufacture of tetraalkylammonium tetrafluoroborate-containing electrolyte compositions |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004039761A1 (en) * | 2002-10-31 | 2004-05-13 | Honeywell Specialty Chemicals Seelze Gmbh | Direct process for the manufacture of tetraalkylammonium tetrafluoroborate-containing electrolyte compositions |
Non-Patent Citations (3)
| Title |
|---|
| ERIC BAKKER ET AL.: 'Lipophilicity of tetraphenylborate derivatives as anionic sites in neutral carrier-based solvent polymeric membranes and lifetime of corresponding ion-selective electrochemical and optical sensors' ANALYTICA CHIMICA ACTA vol. 309, no. ISSUES, 20 June 1995, pages 7 - 17 * |
| KAORU OGURA ET AL.: 'Quaternary Ammonium Tetraarylborates: Substituent Effect in Tetraarylborates on Electric Conductivity in Non-Polar Solvent' ANALYTICAL SCIENCES vol. 17, 2001, pages 341 - 344 * |
| TAKASHI MASADOME: 'Cationic Surfactant-Selective Electrode Based on a Hydrophobic Cation Exchanger' MICROCHIMICA ACTA vol. 140, no. 3-4, 2002, pages 227 - 231 * |
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| Publication number | Publication date |
|---|---|
| WO2010024661A3 (en) | 2010-06-24 |
| MY158538A (en) | 2016-10-14 |
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