Membrane for water filtration

Abstract

The present invention relates to a process for preparing a semipermeable membrane comprising the steps of providing an aqueous phase comprising a multifunctional amine monomer, coating a surface of a porous support membrane with the aqueous phase, applying an organic phase comprising a multifunctional acyl halide monomer, a phosphorous containing compound and a co-solvent, and allowing the multifunctional amine monomer and the multifunctional acyl halide monomer to undergo an interfacial polymerization reaction to form a polyamide thin film composite layer. The presence of the co-solvent in the organic phase together with the phosphorous containing compound enhances the effect of the phosphorous containing compound such that the water flux is increased without substantially sacrificing the salt rejection.

Description

Technical Field

[0001] This disclosure relates to a membrane for water filtration, particularly a membrane form for performing forward osmosis (FO), reverse osmosis (RO), or pressure-assisted forward osmosis (PAFO). This disclosure also relates to the manufacture of the membrane for water filtration and its use in performing forward osmosis operations. Background Technology

[0002] Reverse osmosis (RO) is commonly used to treat water containing dissolved salts. An example of its application is the production of desalinated drinking water from seawater or brackish water. In recent years, forward osmosis (FO) has become increasingly popular. In forward osmosis systems, the feed is typically dehydrated to concentrate the feed stream, while the draw solution is diluted by water migrating across the membrane.

[0003] Membranes used for RO and FO may include a supporting membrane and an active layer attached to the supporting membrane. Optionally, the membrane may also include a third layer, namely a bottom layer typically made of nonwoven polyester fibers. The active layer determines the membrane's characteristics and performance in terms of flux, solute rejection, and fouling tendency. The active layer is typically a polyamide thin film composite (TFC) layer. The polyamide TFC layer can be manufactured on the supporting membrane by interfacial polymerization between a diamine in the aqueous phase and an acyl chloride in the organic phase. Typically, the diamine is 1,3-phenylenediamine (MPD), and the acyl chloride is 1,3,5-phenyltricarboxylic acid chloride (TMC).

[0004] Effective membranes ideally possess both high water flux and high solute rejection. However, these two properties are often mutually exclusive, as denser membranes with smaller pores, requiring higher solute rejection, hinder high water flux. Therefore, extensive research has focused on developing membranes that offer both high water flux and acceptable solute rejection.

[0005] One approach to achieving high water flux is to enhance monomer diffusivity by adding additives to the aqueous phase (i.e., the diamine solution). For example, adding alcohols and ethers to the aqueous phase can result in higher permeate flux and higher salt rejection. The high performance demonstrated by a polyamide membrane prepared by adding 20 wt% isopropanol is a 99.7% rejection rate for 1500 ppm NaCl at 1.5 MPa and a water flux exceeding 1.7 m... 3 / (m 2d) This is approximately 1.7 times that of membranes prepared without isopropanol (see U.S. Patent 5,614,099). Lin Zhao, Philip C.-Y. Chang, W.S. Winston Ho, High-flux reverseosmosis membranes incorporated with hydrophilic additives for brackish waterdesalination, Desalination 308 (2012) 225–232 discloses that the addition of hydrophilic additives to the aqueous phase results in higher water flux and higher salt rejection. The best performance shown by a polyamide membrane prepared by adding 2.85 wt% o-aminobenzoic acid and post-treatment by soaking in an aqueous solution of 5 wt% glycerol and 6 wt% CSA-TEA salt followed by drying at 90 °C for 14 min was a 98.8% rejection rate for 2000 ppm NaCl and a permeate flux exceeding 2.1 m³ / min at 1.55 MPa. 3 / (m 2 d) This is more than twice that of membranes prepared without hydrophilic additives. W. Xie, G. G. Geise, B. D. Freeman, H. S. Lee, G. Byun, J. E. McGrath, Polyamide interfacial composite membranes prepared from m-phenylene diamine, trimesoyl chloride and a new disulfonated diamine, J. Membr. Sci. 403–404 (2012) 152–161 reported that optimizing the concentration between the diamine and acyl chloride resulted in higher permeate flux and higher salt rejection.

[0006] Another approach to achieving higher water flux is to add additives to the organic phase. Byeong-Heon Jeonga, Eric MVHoek, Yushan Yan b, Arun Subramani, Xiaofei Huanga, Gil Hurwitz, Asim K. Ghosha, Anna Jawor, Interfacial polymerization of thin fllm nanocomposites: a new concept for reverse osmosis membranes, J.Membr.Sci.294(2007)1–7 discloses a new membrane concept that is fabricated by adding inorganic nanoscale particles (e.g., zeolite) to the organic phase, resulting in higher permeate flux. C. Kong, A. Koushima, T. Kamada, T. Shintani, M. Kanezashi, T. Yoshioka, T. Tsuru, "Enhanced performance of inorganic–polyamide nanocomposite membranes prepared by metal alkoxide-assisted interfacial polymerization," J. Membr. Sci. 366 (2011) 382–388, discloses higher permeate flux of organic-inorganic hybrid membranes by adding metal alkoxides to the organic phase. The best performance was shown by a polyamide membrane prepared by adding 5 wt% phenyltriethoxysilane with negligible rejection loss. C. Kong, M. Kanezashi, T. Yamamoto, T. Shintani, T. Tsuru, Co-solvent-mediated synthesis of thin polyamide membranes, J. Membr. Sci. 362 (2010) 76–80 and C. Kong, T. Shintani, T. Kamada, V. Freger, T. Tsuru, Co-solvent-mediated synthesis of thin polyamide membranes, J. Membr. Sci. 384 (2011) 10–16 disclose that adding a cosolvent to the organic phase enhances the miscibility at the interface, and that using a model type of polyamide (which is an MPD / TMC polyamide) without adding additives to the aqueous phase results in a high degree of permeate flux.The best performance shown by the polyamide membrane prepared by adding 2 wt% acetone to the organic phase is a glucose rejection of 99.4% for 500 ppm glucose at 1.5 MPa and a water flux of over 1.4 m3 / (m2 d), which is about 4 times that of the membrane prepared without acetone.

[0007] Takashi Kamada, Tomomi Ohara, Takuji Shintani, Toshinori Tsuru, Controlled surface morphology of polyamide membranes via the addition of co-solvent for improved permeate flux, Journal of Membrane Science 467(2014)303–312 discloses the preparation of polyamide membranes with controlled surface morphology via interfacial polymerization, wherein a cosolvent including acetone, ethyl acetate, diethyl ether, toluene, isopropanol (IPA), and N,NO-dimethylformamide (DMF) is added to the organic phase, which allows for control of the surface morphology. Zhaofeng Liu, Guiru Zhu, Yulin Wei, Dapeng Zhang, Lei Jiang, Haizeng Wang, and Congjie Gao, Enhanced flux performance of polyamide composite membranes prepared via interfacial polymerization assisted with ethylformate, Water Science & Technology, 76.7(2017)1884-1894 discloses the addition of ethyl formate as a cosolvent to the organic phase.

[0008] US 6,337,018 B1 discloses a method for preparing a composite membrane, the method comprising the steps of contacting a phosphorus-containing compound with a polyfunctional acyl halide before and / or during a reaction between a polyfunctional acyl halide and a polyfunctional amine to provide an improved membrane with higher flux and / or rejection.

[0009] To save energy, users of membrane modules such as reverse osmosis or forward osmosis need to further optimize semipermeable membranes to increase water flux while maintaining substantially the same solute retention or rejection rate in the feed solution. Summary of the Invention

[0010] In a first aspect, this disclosure relates to a method for preparing a semipermeable membrane, comprising the following steps:

[0011] • Provides an aqueous phase including polyfunctional amine monomers,

[0012] • Cover the surface of the porous support membrane with the aqueous phase.

[0013] • Apply an organic phase comprising polyfunctional acyl halide monomers, phosphorus-containing compounds, and cosolvents, and

[0014] • Allow the polyfunctional amine monomer and the polyfunctional acyl halide monomer to undergo interfacial polymerization to form a polyamide film composite layer.

[0015] The experiments reported in this paper unexpectedly show that the presence of cosolvents in the organic phase, along with phosphorus compounds, enhances the effect of phosphorus compounds, resulting in an increase in water flux compared to membranes containing only phosphorus compounds.

[0016] In a first implementation of the first aspect, the co-solvent is of formula R 1 -OR 2 It means that, among them,

[0017] R 1 Selected from the group consisting of straight-chain or branched C1-C6 lower alkyl, C1-C6 lower alkenyl, or C1-C6 lower alkynyl groups, optionally substituted by one to three substituents independently selected from the group consisting of: methyl, ethyl, propyl, fluorine, chlorine, bromine, iodine, hydroxyl, aldehyde, carboxylic acid, amine, amide, nitrile, methoxy, ethoxy, propoxy, isopropoxy, and any combination thereof, and

[0018] R 2 Selected from the group consisting of: straight-chain or branched C1-C6 lower alkyl, C1-C6 lower alkenyl, C1-C6 lower alkynyl, carbonyl C1-C6 lower alkyl, carbonyl C1-C6 lower alkenyl, carbonyl C1-C6 lower alkynyl, optionally substituted by 1 to 3 substituents selected from the group consisting of: methyl, ethyl or propyl, fluorine, chlorine, bromine, iodine, hydroxyl, aldehyde, carboxylic acid, amine, amide, nitrile, methoxy, ethoxy, propoxy, isopropoxy and any combination thereof.

[0019] In the second implementation of the first aspect, R 1 It is a C1-C6 lower alkyl group and R 2 It is a C1-C6 lower alkyl or carbonyl C1-C6 lower alkyl.

[0020] In a third implementation of the first aspect, the cosolvent is selected from the group consisting of ethyl formate, ethyl acetate, and diethyl ether.

[0021] In a fourth implementation of the first aspect, the co-solvent is a silane or an aromatic compound.

[0022] In the fifth implementation of the first aspect, the silane is of the general formula X3-Si-R 1 This indicates that X is a halogen independently selected from the group consisting of F, Cl, Br, and I, and R... 1 As defined above.

[0023] In the sixth implementation of the first aspect, the R 1 It is a trifluoroC1-C6-alkyl group, such as trifluoropropyl.

[0024] In a seventh implementation of the first aspect, the aromatic compound comprises a benzene ring, which is optionally substituted by one to five substituents selected from the group consisting of: methyl, ethyl, propyl, fluorine, chlorine, bromine, iodine, hydroxyl, aldehyde, carboxylic acid, amine, amide, nitrile, methoxy, ethoxy, propoxy, isopropoxy, and any combination thereof.

[0025] In the eighth implementation of the first aspect, the aromatic compound is mesitylene.

[0026] In a ninth implementation of the first aspect, the phosphorus-containing compound is reacted with the polyfunctional acyl halide prior to the step of reacting the polyfunctional acyl halide and the polyfunctional amine.

[0027] In the tenth implementation, the phosphorus-containing compound has an interaction energy with the polyfunctional acyl halide greater than about 4.0 kcal / mol.

[0028] In the eleventh implementation, the phosphorus-containing compound includes at least one of the following: phosphate ester, phosphite ester, phosphine, phosphine oxide, phosphonate ester, diphosphonate ester, hypophosphite ester, hypophosphite ester, phosphite ester, pyrophosphate ester, pyrophosphoramide, phosphoramide, thiophosphate ester, dithiophosphate ester, and thiophosphoramide ester.

[0029] In the twelfth implementation, the phosphorus-containing compound is represented by the following formula:

[0030]

[0031] Where Z is either the same or different and is selected from: R 2 OP-(R) 2 )2、P(O)-X2、(P(-R 2 )) m -P-X2、(OP(-R 2 )) m -OPR 2 2. (P(O)(-R) 2 )) m-P(O)-R 2 2 and (OP(O)(-R) 2 )) m -OP(O)-R 2 2; P is phosphorus, O is oxygen, m is an integer from 1 to 5; Y is O or a non-bonded electron pair, R 2 As defined above, X is either the same or different and is selected from: R 3 and R 3 -O,R 3 They are the same or different and are selected from H (hydrogen) and a carbon-containing moiety, wherein the carbon-containing moiety is independently selected from R. 2 Group.

[0032] In the thirteenth implementation, the phosphorus-containing compound is selected from the group consisting of: trimethyl phosphate, triethyl phosphate, tributyl phosphate, dibutyl phosphite, bis(2-ethylhexyl) phosphite, triphenylphosphine, triphenyl phosphate, triphenylphosphine, tributyl phosphate, di-tert-butyldiisopropylphosphite, dibutyl butylphosphonate, and trioctylphosphine.

[0033] In the fourteenth implementation, the concentration of the phosphorus-containing compound in the organic phase is 0.2% to 5%.

[0034] In the fifteenth implementation, the concentration of the co-solvent in the organic phase is 0.001 to 5%.

[0035] In the sixteenth implementation, the ratio between the concentrations of the phosphorus-containing compound and the co-solvent in the organic phase is 5:1 to 1:5.

[0036] In the seventeenth implementation, the main solvent of the organic phase includes straight-chain or branched C5-C... 12 Alkanes.

[0037] In the eighteenth implementation, the aqueous phase further includes vesicles having aquaporins introduced therein.

[0038] In the nineteenth implementation, the vesicles include poly-block-(2-methyloxazoline)-poly-block-(dimethylsiloxane) (PMOXA-PDMS) and amine-functionalized poly(dimethylsiloxane) as vesicle membrane forming materials.

[0039] In the twentieth implementation, the support membrane comprises a polysulfone or polyethersulfone polymer.

[0040] In the twenty-first implementation, the porous support membrane is a hollow fiber.

[0041] In a twenty-second implementation, the method includes an additional step of producing a hollow fiber assembly by assembling hollow fiber bundles in a housing, wherein an inlet for delivering a first solution is connected at one end to the inner cavity of the hollow fiber and an outlet is connected at the other end to the inner cavity, and an inlet is provided in the housing for delivering a second solution to an outlet connected to the housing.

[0042] In the twenty-third implementation, the porous support membrane is a flat plate.

[0043] In the twenty-fourth implementation, the method includes an additional step of producing a spiral wound assembly by winding the flat film.

[0044] In a second aspect, the present invention relates to a semipermeable membrane prepared by the above method.

[0045] In a third aspect, the present invention relates to hollow fiber components.

[0046] In a fourth aspect, the present invention relates to spiral winding components.

[0047] In a fifth aspect, the present invention relates to the use of the hollow fiber assembly or the spiral wound assembly for preparing water permeate by reverse osmosis.

[0048] In a sixth aspect, the present invention relates to the use of the hollow fiber assembly or the spiral wound membrane assembly for concentrating a product solution by forward osmosis. Detailed Implementation

[0049] Polyfunctional amine monomers may have primary or secondary amino groups and may be aromatic (e.g., m-phenylenediamine, p-phenylenediamine, 1,3,5-triaminobenzene, 1,3,4-triaminobenzene, 3,5-diaminobenzoic acid, 2,4-diaminotoluene, 2,4-diaminoanisole, and xylenediamine) or aliphatic (e.g., ethylenediamine, propylenediamine, diethylenetriamine, dipropylenetriamine, phenyltriamine, bis(hexamethylene)triamine, bis(hexamethylene)triamine, bis(3-aminopropyl)amine, hexamethylenediamine, N-tartrate dipropylene, 1,3,5-triazine-2,4,6-triamine, and tris(2-diaminoethyl)amine). Suitable polyfunctional amine monomers are diamine or triamine compounds. Examples of preferred polyamines include aromatic primary amines having two or three amino groups, most notably m-phenylenediamine (MPD), and aliphatic secondary amines having two amino groups, most notably piperazine.

[0050] Polyfunctional acyl halide monomers are typically diacyl halides or triacyl halides, selected from trimesoyl chloride (TMC), trimesoyl bromide, isophthaloyl chloride (IPC), isophthaloyl bromide, terephthaloyl chloride (TPC), terephthaloyl bromide, adipic acid chloride, cyanuric chloride, and mixtures thereof. The polyfunctional acyl halide monomer is preferably coated with a nonpolar organic solvent, although polyfunctional acyl halides can be delivered from the gas phase (for polyacyl halides with sufficient vapor pressure). The polyfunctional acyl halide is preferably aromatic in nature and contains at least two, and preferably three, acyl halide groups per molecule. Chlorides are generally preferred over their corresponding bromides or iodides due to their lower cost and greater availability. A preferred polyfunctional acyl group is TMC.

[0051] There are no particular restrictions on phosphorus-containing compounds, and different types of compounds can be used in combination.

[0052] Preferred phosphorus-containing compounds can be represented by the following formula 1:

[0053]

[0054] Where Z is the same or different and is selected from X, OP-(X)2, P(O)-X2, (P(-X))mP-X2, (OP(-X))mOP-X2, (P(O)(-X))mP(O)-X2 and (OP(O)(-X))mOP(O)-X2, where P is phosphorus, O is oxygen, and m is an integer from 1 to 5; Y is O (oxygen) or a non-bonded electron pair, as shown in Equations 2 and 3, respectively.

[0055]

[0056]

[0057] Wherein, X is the same or different and is selected from: R, ROR, or OR, and R is the same or different and is selected from H (hydrogen) and / or carbon-containing moieties. Preferably, Z groups are selected such that together they make the phosphorus-containing compound substantially soluble in organic solutions.

[0058] The phrase “same or different” is intended to mean that individual groups represented by a single symbol (such as “R”) can be different in a given compound. For example, for any given compound, one R group can be hydrogen, while other R groups can be butyl groups.

[0059] The term "carbon-containing moiety" is intended to refer to branched and unbranched acyclic groups, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, 2-pentyl, 3-pentyl, tert-butyl, etc., which can be unsubstituted or substituted (e.g., substituted by amide groups, ether groups, ester groups, sulfone groups, carbonyl groups, acid anhydrides, cyanides, nitriles, isocyanates, carbamates, β-hydroxy esters, double bonds, and triple bonds), as well as cyclic groups, such as cyclopentyl, cyclohexyl, aromatic groups, such as phenyl, heterocyclic, etc., which can be unsubstituted or substituted (e.g., substituted by methyl, ethyl, propyl, hydroxy, amide, ether, sulfone, carbonyl, ester, etc.). Cyclic moiety can be attached to a phosphorus atom by an aliphatic linker (e.g., methyl, ethyl, etc.).

[0060] Preferred carbon-containing moieties include unsubstituted, branched or unbranched C1-C12 groups, and more preferably C1-C8 aliphatic groups, such as methyl, ethyl, propyl, isopropyl, butyl, 2-methylbutyl, 3-methylbutyl, 2-ethylbutyl, pentyl, hexyl, etc. Furthermore, preferred moieties include phenyl groups. Examples of preferred subclasses of phosphorus compounds are represented by formulas 4-9:

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067] R, P, and O are as defined above. Such phosphorus-containing compounds are commercially available or can be synthesized using known methods, see, for example, Whetstone’s U.S. Patent No. 2,648,696 (incorporated herein by reference), and Aharoni et al., Journal of Polymer Science, Volume 22, 2579-2599.

[0068] Examples of applicable classes of phosphorus-containing compounds include: phosphates (e.g., phosphate esters), phosphites, phosphine, phosphine oxide, phosphonates (including diphosphites), hypophosphites, phosphinites, phosphites, pyrophosphates, pyrophosphoramides, phosphoramides, thiophosphates (including dithiophosphates), phosphoroamido thionates, and phosphonothioates (including dithiophosphonodithioates). A non-comprehensive list of specific examples for each class is provided below.

[0069] Specific examples of triphosphates include: trimethyl phosphate, triethyl phosphate, tri(1-propyl) phosphate, tri(2-propyl) phosphate, tri(1-butyl) phosphate, tri(2-butyl) phosphate, tri(1-tert-butyl) phosphate, tri(2-tert-butyl) phosphate, tri(1-pentyl) phosphate, tri(2-pentyl) phosphate, tri(3-pentyl) phosphate, tri(1-hexyl) phosphate, tri(2-hexyl) phosphate, tri(3-hexyl) phosphate, tri(1-heptyl) phosphate, tri(2-heptyl) phosphate, tri(3-heptyl) phosphate, tri(4-heptyl) phosphate, tri(1-octyl) phosphate, tri(2-octyl) phosphate, tri(3-octyl) phosphate, tri(4-octyl) phosphate, and phosphate. Tris(1-CH3(CH2)8) phosphate, Tris(2-CH3(CH2)8) phosphate, Tris(3-CH3(CH2)8) phosphate, Tris(4-CH3(CH2)8) phosphate, Tris(1-CH3(CH2)9) phosphate, Tris(2-CH3(CH2)9) phosphate, Tris(3-CH3(CH2)9) phosphate, Tris(4-CH3(CH2)9) phosphate, Tris(5-CH3(CH2)9) phosphate, Tris(1-CH3(CH2)10) phosphate, Tris(2-CH3(CH2)10) phosphate, Tris(3-CH3(CH2)10) phosphate, Tris(4-CH3(CH2)10) phosphate, Tris(5-CH3(CH2) 10) esters, tris(1-CH3(CH2)11) phosphate, tris(2-CH3(CH2)11) phosphate, tris(3-CH3(CH2)11) phosphate, tris(4-CH3(CH2)11) phosphate, tris(5-CH3(CH2)11) phosphate, tris(6-CH3(CH2)11) phosphate, tris(1-CH3(CH2)12) phosphate, tris(2-CH3(CH2)12) phosphate, tris(3-CH3(CH2)12) phosphate, tris(4-CH3(CH2)12) phosphate, tris(5-CH3(CH2)12) phosphate, tris(6-CH3(CH2)12) phosphate, tris(methylpentyl) phosphate, tris(ethyl) phosphate Tris(methylhexyl) phosphate, Tris(ethylhexyl) phosphate, Tris(propylhexyl) phosphate, Tris(methylheptyl) phosphate, Tris(ethylheptyl) phosphate, Tris(diethylheptyl) phosphate, Tris(methyloctyl) phosphate, Tris(dimethyloctyl) phosphate, Methyl di-(-ethyl) phosphate, Methyl di-(1-propyl) phosphate, Methyl di-(2-propyl) phosphate, Methyl di-(1-butyl) phosphate, Methyl di-(2-butyl) phosphate, Methyl di-(1-tert-butyl) phosphate, Methyl di-(2-tert-butyl) phosphate, Methyl di-(1-pentyl) phosphate, Methyl di-(2-pentyl) phosphate, Methyl di-(3-pentyl) phosphate, Methyl di-(1-hexyl) phosphateMethyl di-(2-hexyl) phosphate, methyl di-(3-hexyl) phosphate, methyl di-(1-heptyl) phosphate, methyl di-(2-heptyl) phosphate, methyl di-(3-heptyl) phosphate, methyl di-(4-heptyl) phosphate, methyl di-(1-octyl) phosphate, methyl di-(2-octyl) phosphate, methyl di-(3-octyl) phosphate, methyl di-(4-octyl) phosphate, methyl di-(1-CH3(CH2)8) phosphate, methyl di-(2-CH3(CH2)8) phosphate, methyl di-(3-CH3(CH2)8) phosphate, methyl di-(4-CH3(CH2)8) phosphate, methyl di-(1-CH3(CH2)9) phosphate, phosphorus Methyl di-(2-CH3(CH2)9) ester, methyl di-(3-CH3(CH2)9) ester, methyl di-(4-CH3(CH2)9) ester, methyl di-(5-CH3(CH2)9) ester, methyl di-(1-CH3(CH2)10) ester, methyl di-(2-CH3(CH2)10) ester, methyl di-(3-CH3(CH2)10) ester, methyl di-(4-CH3(CH2)10) ester, methyl di-(5-CH3(CH2)10) ester, methyl di-(1-CH3(CH2)11) ester, methyl di-(2-CH3(CH2)11) ester, methyl di-(3-) ester methyl di-(4-CH3(CH2)11) ester, methyl di-(5-CH3(CH2)11) ester, methyl di-(6-CH3(CH2)11) ester, methyl di-(1-CH3(CH2)12) ester, methyl di-(2-CH3(CH2)12) ester, methyl di-(3-CH3(CH2)12) ester, methyl di-(4-CH3(CH2)12) ester, methyl di-(5-CH3(CH2)12) ester, methyl di-(6-CH3(CH2)12) ester, ethyl di-(1-propyl) ester, ethyl di-(2-propyl) ester, ethyl di-( 1-Butyl) ester, Ethyl di-(2-butyl) phosphate, Ethyl di-(1-tert-butyl) phosphate, Ethyl di-(2-tert-butyl) phosphate, Ethyl di-(1-pentyl) phosphate, Ethyl di-(2-pentyl) phosphate, Ethyl di-(3-pentyl) phosphate, Ethyl di-(1-hexyl) phosphate, Ethyl di-(2-hexyl) phosphate, Ethyl di-(3-hexyl) phosphate, Ethyl di-(1-heptyl) phosphate, Ethyl di-(2-heptyl) phosphate, Ethyl di-(3-heptyl) phosphate, Ethyl di-(4-heptyl) phosphate, Ethyl di-(1-octyl) phosphate, Ethyl di-(2-octyl) phosphate, Ethyl di-(3-octyl) phosphate, Ethyl di-(4-octyl) phosphate,Ethyl di-(1-CH3(CH2)8) phosphate, ethyl di-(2-CH3(CH2)8) phosphate, ethyl di-(3-CH3(CH2)8) phosphate, ethyl di-(4-CH3(CH2)8) phosphate, ethyl di-(1-CH3(CH2)9) phosphate, ethyl di-(2-CH3(CH2)9) phosphate, ethyl di-(3-CH3(CH2)9) phosphate, ethyl di-(4-CH3(CH2)9) phosphate, ethyl di-(5-CH3(CH2)9) phosphate, ethyl di-(1-CH3(CH2)10) phosphate, ethyl di-(2-CH3(CH2)10) phosphate, ethyl di-(3-CH3(CH2)10) phosphate, ethyl di-(3-CH3(CH2)10) phosphate, ethyl di-(3-CH3(CH2)10) phosphate, ethyl di-(3-CH3(CH2)10) phosphate, ethyl di-(3-CH3(CH2)10) phosphate, ethyl di-(4-CH3(CH2)8) phosphate, ethyl di-(1-CH3(CH2)9) phosphate, ethyl di-(2-CH3(CH2)10) phosphate, ethyl di-(3-CH3(CH2)10) phosphate, ethyl di-(3-CH3(CH2)10) phosphate, ethyl di-(4-CH3(CH2)9) phosphate, ethyl di-(1-CH3(CH2)9) phosphate, ethyl di-(2 ... Ethyl di-(4-CH3(CH2)10) ester, ethyl di-(5-CH3(CH2)10) ester, ethyl di-(1-CH3(CH2)11) ester, ethyl di-(2-CH3(CH2)11) ester, ethyl di-(3-CH3(CH2)11) ester, ethyl di-(4-CH3(CH2)11) ester, ethyl di-(5-CH3(CH2)11) ester, ethyl di-(6-CH3(CH2)11) ester, ethyl di-(1-CH3(CH2)12) ester, ethyl di-(2-CH3(CH2)12) ester, ethyl di-(3-CH3(CH2)11) ester 12) Ester, Ethyl di-(4-CH3(CH2)12) phosphate, Ethyl di-(5-CH3(CH2)12) phosphate, Ethyl di-(6-CH3(CH2)12) phosphate, 1-propyl di-(2-propyl) phosphate, 1-propyl di-(1-butyl) phosphate, 1-propyl di-(2-butyl) phosphate, 1-propyl di-(1-tert-butyl) phosphate, 1-propyl di-(2-tert-butyl) phosphate, 1-propyl di-(1-pentyl) phosphate, 1-propyl di-(2-pentyl) phosphate, 1-propyl di-(3-pentyl) phosphate, 1-propyl di-(1-hexyl) phosphate, 1-propyl di-(2-hexyl) phosphate, 1-propyl di-(3-hexyl) phosphate 1-propyl di-(1-heptyl) phosphate, 1-propyl di-(2-heptyl) phosphate, 1-propyl di-(3-heptyl) phosphate, 1-propyl di-(4-heptyl) phosphate, 1-propyl di-(1-octyl) phosphate, 1-propyl di-(2-octyl) phosphate, 1-propyl di-(3-octyl) phosphate, 1-propyl di-(4-octyl) phosphate, 1-propyl di-(1-CH3(CH2)8) phosphate, 1-propyl di-(2-CH3(CH2)8) phosphate, 1-propyl di-(3-CH3(CH2)8) phosphate, 1-propyl di-(4-CH3(CH2)8) phosphate, 1-propyl di-(1-CH3(CH2)9) phosphate,1-Propyl di-(2-CH3(CH2)9) phosphate, 1-Propyl di-(3-CH3(CH2)9) phosphate, 1-Propyl di-(4-CH3(CH2)9) phosphate, 1-Propyl di-(5-CH3(CH2)9) phosphate, 1-Propyl di-(1-CH3(CH2)10) phosphate, 1-Propyl di-(2-CH3(CH2)10) phosphate, 1-Propyl di-(3-CH3(CH2)10) phosphate, 1-Propyl di-(4-CH3(CH2)10) phosphate, 1-Propyl di-(5-CH3(CH2)10) phosphate, 1-Propyl di-(1-CH3(CH2)11) phosphate, 1-Propyl di-(2-CH2)11) phosphate, 1-Propyl di-(2-CH2)10) phosphate 1-Propyl di-(3-CH3(CH2)11) ester, 1-Propyl di-(4-CH3(CH2)11) ester, 1-Propyl di-(5-CH3(CH2)11) ester, 1-Propyl di-(6-CH3(CH2)11) ester, 1-Propyl di-(1-CH3(CH2)12) ester, 1-Propyl di-(2-CH3(CH2)12) ester, 1-Propyl di-(3-CH3(CH2)12) ester, 1-Propyl di-(4-CH3(CH2)12) ester, 1-Propyl di-(5-CH3(CH2)12) ester, 1-Propyl di-(6-CH3(CH2)12) ester Ester, 2-propyl di-(1-butyl) phosphate, 2-propyl di-(2-butyl) phosphate, 2-propyl di-(1-tert-butyl) phosphate, 2-propyl di-(2-tert-butyl) phosphate, 2-propyl di-(1-pentyl) phosphate, 2-propyl di-(2-pentyl) phosphate, 2-propyl di-(3-pentyl) phosphate, 2-propyl di-(1-hexyl) phosphate, 2-propyl di-(2-hexyl) phosphate, 2-propyl di-(3-hexyl) phosphate, 2-propyl di-(1-heptyl) phosphate, 2-propyl di-(2-heptyl) phosphate, 2-propyl di-(3-heptyl) phosphate, 2-propyl di-(4-heptyl) phosphate, 2-propyl di-(1-octyl) phosphate, 2-propyl 2-propyl di-(2-octyl) ester, 2-propyl di-(3-octyl) ester, 2-propyl di-(4-octyl) ester, 2-propyl di-(1-CH3(CH2)8) ester, 2-propyl di-(2-CH3(CH2)8) ester, 2-propyl di-(3-CH3(CH2)8) ester, 2-propyl di-(4-CH3(CH2)8) ester, 2-propyl di-(1-CH3(CH2)9) ester, 2-propyl di-(2-CH3(CH2)9) ester, 2-propyl di-(3-CH3(CH2)9) ester, 2-propyl di-(4-CH3(CH2)9) ester, 2-propyl di-(5-CH3(CH2)9) ester,2-propyl di-(1-CH3(CH2)10) phosphate, 2-propyl di-(2-CH3(CH2)10) phosphate, 2-propyl di-(3-CH3(CH2)10) phosphate, 2-propyl di-(4-CH3(CH2)10) phosphate, 2-propyl di-(5-CH3(CH2)10) phosphate, 2-propyl di-(1-CH3(CH2)11) phosphate, 2-propyl di-(2-CH3(CH2)11) phosphate, 2-propyl di-(3-CH3(CH2)11) phosphate, 2-propyl di-(4-CH3(CH2)11) phosphate, 2-propyl di-(5-CH3(CH2)11) phosphate, 2-propyl di-( 6-CH3(CH2)11) ester, 2-propyl di-(1-CH3(CH2)12) ester, 2-propyl di-(2-CH3(CH2)12) ester, 2-propyl di-(3-CH3(CH2)12) ester, 2-propyl di-(4-CH3(CH2)12) ester, 2-propyl di-(5-CH3(CH2)12) ester, 2-propyl di-(6-CH3(CH2)12) ester, butyl di-(1-tert-butyl) ester, butyl di-(2-tert-butyl) ester, butyl di-(1-pentyl) ester, butyl di-(2-pentyl) ester, butyl di-(3-pentyl) ester, butyl di-(1-hexyl) ester, butyl di- 2-Hexyl phosphate, butyl di-(3-hexyl) phosphate, butyl di-(1-heptyl) phosphate, butyl di-(2-heptyl) phosphate, butyl di-(3-heptyl) phosphate, butyl di-(4-heptyl) phosphate, butyl di-(1-octyl) phosphate, butyl di-(2-octyl) phosphate, butyl di-(3-octyl) phosphate, butyl di-(4-octyl) phosphate, butyl di-(1-CH3(CH2)8) phosphate, butyl di-(2-CH3(CH2)8) phosphate, butyl di-(3-CH3(CH2)8) phosphate, butyl di-(4-CH3(CH2)8) phosphate, butyl di-(1-CH3(CH2)9) phosphate, butyl di-(2-C Butyl phosphate di-(3-CH3(CH2)9) ester, butyl phosphate di-(4-CH3(CH2)9) ester, butyl phosphate di-(5-CH3(CH2)9) ester, butyl phosphate di-(1-CH3(CH2)10) ester, butyl phosphate di-(2-CH3(CH2)10) ester, butyl phosphate di-(3-CH3(CH2)10) ester, butyl phosphate di-(4-CH3(CH2)10) ester, butyl phosphate di-(5-CH3(CH2)10) ester, butyl phosphate di-(1-CH3(CH2)11) ester, butyl phosphate di-(2-CH3(CH2)11) ester, butyl phosphate di-(3-CH3(CH2)11) esterButyl di-(4-CH3(CH2)11) phosphate, butyl di-(5-CH3(CH2)11) phosphate, butyl di-(6-CH3(CH2)11) phosphate, butyl di-(1-CH3(CH2)12) phosphate, butyl di-(2-CH3(CH2)12) phosphate, butyl di-(3-CH3(CH2)12) phosphate, butyl di-(4-CH3(CH2)12) phosphate, butyl di-(5-CH3(CH2)12) phosphate, butyl di-(6-CH3(CH2)12) phosphate, methyl ethyl propyl phosphate, methyl ethyl butyl phosphate, methyl ethyl pentyl phosphate, methyl ethyl hexyl phosphate, methyl ethyl heptyl phosphate Ester, methyl ethyl octyl phosphate, methyl propyl butyl phosphate, methyl propyl pentyl phosphate, methyl propyl hexyl phosphate, methyl propyl heptyl phosphate, methyl propyl octyl phosphate, methyl butyl pentyl phosphate, methyl butyl hexyl phosphate, methyl butyl heptyl phosphate, methyl butyl octyl phosphate, methyl pentyl heptyl phosphate, methyl pentyl octyl phosphate, methyl hexyl heptyl phosphate, methyl hexyl octyl phosphate, ethyl propyl butyl phosphate, ethyl propyl pentyl phosphate, ethyl propyl heptyl phosphate, ethyl propyl octyl phosphate, ethyl butyl pentyl phosphate, ethyl butyl hexyl phosphate, ethyl butyl heptyl phosphate, ethyl butyl octyl phosphate, ethyl pentyl phosphate Hexyl phosphate, ethylpentylheptyl phosphate, ethylpentyloctyl phosphate, ethylhexylheptyl phosphate, ethylhexyloctyl phosphate, triphenyl phosphate, methyl di-phenyl phosphate, ethyl di-phenyl phosphate, 1-propyl di-phenyl phosphate, 2-propyl di-phenyl phosphate, 1-butyl di-phenyl phosphate, 2-butyl di-phenyl phosphate, 1-tert-butyl di-phenyl phosphate, 2-tert-butyl di-phenyl phosphate, 1-pentyl di-phenyl phosphate, 2-pentyl di-phenyl phosphate, 3-pentyl di-phenyl phosphate, 1-hexyl di-phenyl phosphate, 2-hexyl di-phenyl phosphate, 3-hexyl di-phenyl phosphate, 1-heptyl di-phenyl phosphate, 2-heptyl di-phenyl phosphate, 3-heptyl di-phenyl phosphate, 4-heptyl di-phenyl phosphate Octyl diphenyl phosphate, 1-octyl diphenyl phosphate, 2-octyl diphenyl phosphate, 3-octyl diphenyl phosphate, 4-octyl diphenyl phosphate, 1CH3(CH2)8 diphenyl phosphate, 2CH3(CH2)8 diphenyl phosphate, 3CH3(CH2)8 diphenyl phosphate, 4CH3(CH2)8 diphenyl phosphate, 1CH3(CH2)9 diphenyl phosphate, 2CH3(CH2)9 diphenyl phosphate, 3CH3(CH2)9 diphenyl phosphate, 4CH3(CH2)9 diphenyl phosphate, 5CH3(CH2)9 diphenyl phosphate, 1CH3(CH2)10 diphenyl phosphate, 2CH3(CH2)10 diphenyl phosphate3CH3(CH2)10 di-phenyl phosphate, 4CH3(CH2)10 di-phenyl phosphate, 5CH3(CH2)10 di-phenyl phosphate, 1CH3(CH2)11 di-phenyl phosphate, 2CH3(CH2)11 di-phenyl phosphate, 3CH3(CH2)11 di-phenyl phosphate, 4CH3(CH2)11 di-phenyl phosphate, 5CH3(CH2)11 di-phenyl phosphate, 6CH3(CH2)11 di-phenyl phosphate, 1CH3(CH2)12 di-phenyl phosphate, 2CH3(CH2)12 di-phenyl phosphate, 3CH3(CH2)12 di-phenyl phosphate, 4CH3(CH2)12 di-phenyl phosphate 5CH3(CH2)12 di-phenyl phosphate, 6CH3(CH2)12 di-phenyl phosphate, dimethyl phenyl phosphate, diethyl phenyl phosphate, di(1-propyl)phenyl phosphate, di(2-propyl)phenyl phosphate, di(-isopropyl)phenyl phosphate, di(1-butyl)phenyl phosphate, di(2-butyl)phenyl phosphate, di(1-tert-butyl)phenyl phosphate, di(2-tert-butyl)phenyl phosphate, di(1-pentyl)phenyl phosphate, di(2-pentyl)phenyl phosphate, di(3-pentyl)phenyl phosphate, di(1-hexyl)phenyl phosphate, di(2-hexyl)phenyl phosphate, di(3-hexyl)phenyl phosphate, di(1-heptyl)phenyl phosphate, di(2-heptyl)phenyl phosphate Di(3-heptyl)phenyl phosphate, di(4-heptyl)phenyl phosphate, di(1-octyl)phenyl phosphate, di(2-octyl)phenyl phosphate, di(3-octyl)phenyl phosphate, di(4-octyl)phenyl phosphate, di(1-CH3(CH2)8)phenyl phosphate, di(2-CH3(CH2)8)phenyl phosphate, di(3-CH3(CH2)8)phenyl phosphate, di(4-CH3(CH2)8)phenyl phosphate, di(1-CH3(CH2)9)phenyl phosphate, di(2-CH3(CH2)9)phenyl phosphate, di(3-CH3(CH2)9)phenyl phosphate, di(4 ... (5-CH3(CH2)9)phenyl phosphate, di(1-CH3(CH2)10)phenyl phosphate, di(2-CH3(CH2)10)phenyl phosphate, di(3-CH3(CH2)10)phenyl phosphate, di(4-CH3(CH2)10)phenyl phosphate, di(5-CH3(CH2)10)phenyl phosphate, di(1-CH3(CH2)11)phenyl phosphate, di(2-CH3(CH2)11)phenyl phosphate, di(3-CH3(CH2)11)phenyl phosphate, di(4-CH3(CH2)11)phenyl phosphate, di(5-CH3(CH2)11)phenyl phosphate, di(6-CH3(CH2)11)phenyl phosphateDi(1-CH3(CH2)12)phenyl phosphate, Di(2-CH3(CH2)12)phenyl phosphate, Di(3-CH3(CH2)12)phenyl phosphate, Di(4-CH3(CH2)12)phenyl phosphate, Di(5-CH3(CH2)12)phenyl phosphate, Di(6-CH3(CH2)12)phenyl phosphate, Triethylene phosphate, Tri(1-propene) phosphate, Tri(2-propene) phosphate, Tri(3-propene) phosphate, Tri(1-(1-butene)) phosphate, Tri(2-(1-butene)) phosphate, Tri... (3-(1-butene)) ester, tris(4-(1-butene)) ester, tris(1-(2-butene)) ester, tris(2-(2-butene)) ester, tris(3-(2-butene)) ester, tris(4-(2-butene)) ester, tris(1-(1-pentene)) ester, tris(2-(1-pentene)) ester, tris(3-(1-pentene)) ester, tris(4-(2-butene)) ester, tris(1-(1-pentene)) ester, tris(2-(2-pentene)) ester, tris(3-(1-butene)) ester, tris(4-(1-butene)) ester, tris(1 ...5-(1-pentene)) ester, tris(1-(2-pentene)) ester, tris(3-(1-butene)) ester, tris(4-(1-butene)) ester, tris(5-(1-pentene)) ester, tris(1-(2-pentene)) ester, tris(3-(1-butene)) ester, tris(4-(1-butene)) ester, tris( 2-Pentene phosphate, Tris(4-(2-pentene)) phosphate, Tris(5-(2-pentyl)) phosphate, Tris(1-(1-hexene)) phosphate, Tris(2-(1-hexene)) phosphate, Tris(3-(1-hexene)) phosphate, Tris(4-(1-hexene)) phosphate, Tris(5-(1-hexene)) phosphate, Tris(6-(1-hexene)) phosphate, Tris(1-(3-hexene)) phosphate, Tris(2-(3-hexene)) phosphate, Tris(3-(3-hexene)) phosphate, Tris(4-(3-hexene)) phosphate, Tris(5-(3-hexene)) phosphate Tris(6-(3-hexene)) phosphate, tris(1-(2-hexene)) phosphate, tris(2-(2-hexene)) phosphate, tris(3-(2-hexene)) phosphate, tris(4-(2-hexene)) phosphate, tris(5-(2-hexene)) phosphate, tris(6-(2-hexene)) phosphate, tris(phenylmethyl) phosphate, tris(2-methylphenyl) phosphate, tris(3-methylphenyl) phosphate, tris(4-methylphenyl) phosphate, tris(2-ethylphenyl) phosphate, tris(3-ethylphenyl) phosphate, and tris(4-ethylphenyl) phosphate.

[0070] Specific examples of phosphate diesters include: dimethyl phosphate, diethyl phosphate, di(1-propyl) phosphate, di(2-propyl) phosphate, di(1-butyl) phosphate, di(2-butyl) phosphate, di(1-tert-butyl) phosphate, di(2-tert-butyl) phosphate, di(1-pentyl) phosphate, di(2-pentyl) phosphate, di(3-pentyl) phosphate, di(1-hexyl) phosphate, di(2-hexyl) phosphate, di(3-hexyl) phosphate, di(1-heptyl) phosphate, di(2-heptyl) phosphate, di(3-heptyl) phosphate, di(4-heptyl) phosphate, di(1-octyl) phosphate, di(2-octyl) phosphate, di(3-octyl) phosphate, di(4-octyl) phosphate, and phosphate. Di(1-CH3(CH2)8) phosphate, di(2-CH3(CH2)8) phosphate, di(3-CH3(CH2)8) phosphate, di(4-CH3(CH2)8) phosphate, di(1-CH3(CH2)9) phosphate, di(2-CH3(CH2)9) phosphate, di(3-CH3(CH2)9) phosphate, di(4-CH3(CH2)9) phosphate, di(5-CH3(CH2)9) phosphate, di(1-CH3(CH2)10) phosphate, di(2-CH3(CH2)10) phosphate, di(3-CH3(CH2)10) phosphate, di(4-CH3(CH2)10) phosphate, di(5-CH3(CH2)9) phosphate 10) esters, di(1-CH3(CH2)11) phosphate, di(2-CH3(CH2)11) phosphate, di(3-CH3(CH2)11) phosphate, di(4-CH3(CH2)11) phosphate, di(5-CH3(CH2)11) phosphate, di(6-CH3(CH2)11) phosphate, di(1-CH3(CH2)12) phosphate, di(2-CH3(CH2)12) phosphate, di(3-CH3(CH2)12) phosphate, di(4-CH3(CH2)12) phosphate, di(5-CH3(CH2)12) phosphate, di(6-CH3(CH2)12) phosphate, di(1-(methylpentyl)) phosphate, phosphate Di(2-(methylpentyl)) phosphate, di(3-(methylpentyl)) phosphate, di(1-(di-methylpentyl)) phosphate, di(2-(di-methylpentyl)) phosphate, di(3-(di-methylpentyl)) phosphate, di(1-(ethylpentyl)) phosphate, di(2-(ethylpentyl)) phosphate, di(3-(ethylpentyl)) phosphate, di(1-(methylhexyl)) phosphate, di(2-(methylhexyl)) phosphate, di(3-(methylhexyl)) phosphate, di(1-(di-methylhexyl)) phosphate, di(2-(di-methylhexyl)) phosphate, di(3-(di-methylhexyl)) phosphate, di(1-(ethylhexyl)) phosphate, di(2-(ethylhexyl)) phosphateDi(3-(ethylhexyl)) phosphate, di(methylheptayl) phosphate, di(di-methylheptayl) phosphate, di(ethylheptayl) phosphate, di(methyloctyl) phosphate, di(di-methyloctyl) phosphate, di(ethyloctyl) phosphate, methyl ethyl phosphate, methyl propyl phosphate, methyl butyl phosphate, methyl tert-butyl phosphate, methyl pentyl phosphate, methyl hexyl phosphate, methyl heptayl phosphate, methyl octyl phosphate, methyl CH3(CH2)8 phosphate, methyl CH3(CH2)9 phosphate, methyl CH3(CH2)10 phosphate, methyl CH3(CH2)11 phosphate, phosphorus Methyl phosphate CH3(CH2)12 ester, ethyl propyl phosphate, ethyl butyl phosphate, ethyl tert-butyl phosphate, ethyl pentyl phosphate, ethyl hexyl phosphate, ethyl heptyl phosphate, ethyl octyl phosphate, ethyl CH3(CH2)8 ester, ethyl CH3(CH2)9 ester, ethyl CH3(CH2)10 ester, ethyl CH3(CH2)11 ester, ethyl CH3(CH2)12 ester, propyl butyl phosphate, propyl tert-butyl phosphate, propyl pentyl phosphate, propyl hexyl phosphate, propyl heptyl phosphate, propyl octyl phosphate, propyl CH3(CH2)8 ester propyl phosphate CH3(CH2)9 ester, propyl phosphate CH3(CH2)10 ester, propyl phosphate CH3(CH2)11 ester, propyl phosphate CH3(CH2)12 ester, butyl tert-butyl phosphate, butyl tert-pentyl phosphate, butyl tert-butylhexyl phosphate, butyl tert-butylheptyl phosphate, butyl tert-butyloctyl phosphate, butyl tert-butyl CH3(CH2)8 ester, butyl tert-butyl CH3(CH2)9 ester, butyl tert-butyl CH3(CH2)10 ester, butyl tert-butyl CH3(CH2)11 ester, butyl tert-butyl CH3(CH2)12 ester, pentylhexyl phosphate, pentylheptyl phosphate, pentyloctyl phosphate The following are listed as esters: pentyl phosphate CH3(CH2)8 ester, pentyl phosphate CH3(CH2)9 ester, pentyl phosphate CH3(CH2)10 ester, pentyl phosphate CH3(CH2)11 ester, pentyl phosphate CH3(CH2)12 ester, hexyl heptahydrate phosphate, hexyl octyl phosphate, dibutylene phosphate, dipentenene phosphate, dihexenene phosphate, diheptenene phosphate, and di-octenene phosphate.

[0071] Specific examples of monophosphate esters include: methyl phosphate, ethyl phosphate, propyl phosphate, butyl phosphate, pentyl phosphate, hexyl phosphate, heptyl phosphate, octyl phosphate, CH3(CH2)8 phosphate, CH3(CH2)9 phosphate, CH3(CH2)10 phosphate, CH3(CH2)11 phosphate, CH3(CH2)12 phosphate, methylpropyl phosphate, methyl butyl phosphate, methyl pentyl phosphate, methyl hexyl phosphate, methyl heptyl phosphate, methyl octyl phosphate, methyl CH3(CH2)8 phosphate, methyl CH3(CH2)9 phosphate, methyl CH3(CH2)10 phosphate, methyl CH3(CH2)11 phosphate, methyl CH3(CH2)12 phosphate, dimethyl butyl phosphate, dimethyl phosphate, dimethyl phosphate Methyl pentyl phosphate, dimethyl hexyl phosphate, dimethyl heptayl phosphate, dimethyl octyl phosphate, dimethyl CH3(CH2)8 phosphate, dimethyl CH3(CH2)9 phosphate, dimethyl CH3(CH2)10 phosphate, dimethyl CH3(CH2)11 phosphate, dimethyl CH3(CH2)12 phosphate, ethyl butyl phosphate, ethyl pentyl phosphate, ethyl hexyl phosphate, ethyl heptayl phosphate, ethyl octyl phosphate, ethyl CH3(CH2)8 phosphate, ethyl CH3(CH2)9 phosphate, ethyl CH3(CH2)10 phosphate, ethyl CH3(CH2)11 phosphate, ethyl CH3(CH2)12 phosphate, butenyl phosphate, pentenyl phosphate, hexenyl phosphate, heptayl phosphate, and octenyl phosphate.

[0072] For the sake of brevity, a complete list of phosphites is not provided; however, applicable phosphite substances correspond to each of the triphosphate, diephosphate, and monophosphate esters provided in the preceding paragraphs. For example, by simply replacing the word "phosphate ester" with "phosphite" in the preceding paragraphs, one can quickly generate a list of representative phosphite substances applicable to the present invention.

[0073] Examples of phosphine compounds include:

[0074] Tri-(1-hexyl)phosphine, tri-(2-hexyl)phosphine, tri-(3-hexyl)phosphine, tri-(1-heptyl)phosphine, tri-(2-heptyl)phosphine, tri-(3-heptyl)phosphine, tri-(4-heptyl)phosphine, tri-(1-octyl)phosphine, tri-(2-octyl)phosphine, tri-(3-octyl)phosphine, tri-(4-octyl)phosphine, tri-(1-CH3(CH2)8)phosphine, tri-(2-CH3(CH2)8)phosphine, tri-(3-CH3(CH2)8)phosphine, tri-(4-CH3(CH2)8)phosphine, tri-(1-CH3(CH2)9)phosphine, tri-(2-CH3(CH2)9)phosphine, tri-(3-CH13(CH2)9)phosphine, tri-(4-CH3(CH2)9)phosphine, tri- -(5-CH3(CH2)9)phosphine, tri-(1-CH3(CH2)10)phosphine, tri-(2-CH3(CH2)10)phosphine, tri-(3-CH3(CH2)10)phosphine, tri-(4-CH3(CH2)10)phosphine, tri-(5-CH3(CH2)10)phosphine, tri-(1-CH3(CH2)11)phosphine, tri-(2-CH3(CH2)11)phosphine, tri-(3-CH3(CH2)11)phosphine, tri-(4-CH3(CH2)11)phosphine, tri-(5-CH3(CH2)11)phosphine, tri-(6-CH3(CH2)11)phosphine, tri-(1-CH3(CH2)12)phosphine, tri-(2-CH3(CH2)12)phosphine Phosphine, tri-(3-CH3(CH2)12)phosphine, tri-(4-CH3(CH2)12)phosphine, tri-(5-CH3(CH2)12)phosphine, tri-(6-CH3(CH2)12)phosphine, methyl di-(1-hexyl)phosphine, methyl di-(2-hexyl)phosphine, methyl di-(3-hexyl)phosphine, methyl di-(1-heptyl)phosphine, methyl di-(2-heptyl)phosphine, methyl di-(3-heptyl)phosphine, methyl di-(4-heptyl)phosphine, methyl di-(1-octyl)phosphine, methyl di-(2-octyl)phosphine, methyl di-(3-octyl)phosphine, methyl di-(4-octyl)phosphine, methyl di-(1-CH3(CH2)8)phosphine, methyl di-(2-CH3(CH2)8)phosphine, methyl di- (3-CH3(CH2)8)phosphine, methyldi-(4-CH3(CH2)8)phosphine, methyldi-(1-CH3(CH2)9)phosphine, methyldi-(2-CH3(CH2)9)phosphine, methyldi-(3-CH3(CH2)9)phosphine, methyldi-(4-CH3(CH2)9)phosphine, methyldi-(5-CH3(CH2)9)phosphine, methyldi-(1-CH3(CH2)10)phosphine, methyldi-(2-CH3(CH2)10)phosphine, methyldi-(3-CH3(CH2)10)phosphine, methyldi-(4-CH3(CH2)10)phosphine, methyldi-(5-CH3(CH2)10)phosphine, methyldi-(1-CH3(CH2)11)phosphineMethyldi-(2-CH3(CH2)11)phosphine, methyldi-(3-CH3(CH2)11)phosphine, methyldi-(4-CH3(CH2)11)phosphine, methyldi-(5-CH3(CH2)11)phosphine, methyldi-(6-CH3(CH2)11)phosphine, methyldi-(1-CH3(CH2)12)phosphine, methyldi-(2-CH3(CH2)12)phosphine, methyldi-(3-CH3(CH2)12)phosphine, methyldi-(4-CH3(CH2)12)phosphine, methyldi-(5-CH3(CH2)12)phosphine, methyldi-(6-CH3(CH2)12)phosphine, ethyldi-(1-hexyl)phosphine, ethyldi-(2-hexyl)phosphine, ethyldi- -(3-hexyl)phosphine, ethyl di-(1-heptyl)phosphine, ethyl di-(2-heptyl)phosphine, ethyl di-(3-heptyl)phosphine, ethyl di-(4-heptyl)phosphine, ethyl di-(1-octyl)phosphine, ethyl di-(2-octyl)phosphine, ethyl di-(3-octyl)phosphine, ethyl di-(4-octyl)phosphine, ethyl di-(1-CH3(CH2)8)phosphine, ethyl di-(2-CH3(CH2)8)phosphine, ethyl di-(3-CH3(CH2)8)phosphine, ethyl di-(4-CH3(CH2)8)phosphine, ethyl di-(1-CH3(CH2)9)phosphine, ethyl di-(2-CH3(CH2)9)phosphine, ethyl di-(3-CH3(CH2)9)phosphine, ethyl di-(4-CH2)8)phosphine, ethyl di-(1-CH3(CH2)9)phosphine, ethyl di-(2-CH3(CH2)9)phosphine, ethyl di-(3-CH3(CH2)9)phosphine, ethyl di-(4-CH2)8)phosphine 3(CH2)9)phosphine, ethyldi-(5-CH3(CH2)9)phosphine, ethyldi-(1-CH3(CH2)10)phosphine, ethyldi-(2-CH3(CH2)10)phosphine, ethyldi-(3-CH3(CH2)10)phosphine, ethyldi-(4-CH3(CH2)10)phosphine, ethyldi-(5-CH3(CH2)10)phosphine, ethyldi-(1-CH3(CH2)11)phosphine, ethyldi-(2-CH3(CH2)11)phosphine, ethyldi-(3-CH3(CH2)11)phosphine, ethyldi-(4-CH3(CH2)11)phosphine, ethyldi-(5-CH3(CH2)11)phosphine, ethyldi-(6-CH3(CH2)11)phosphine Phosphorus, Ethyl di-(1-CH3(CH2)12)phosphine, Ethyl di-(2-CH3(CH2)12)phosphine, Ethyl di-(3-CH3(CH2)12)phosphine, Ethyl di-(4-CH3(CH2)12)phosphine, Ethyl di-(5-CH3(CH2)12)phosphine, Ethyl di-(6-CH3(CH2)12)phosphine, 1-propyl di-(1-hexyl)phosphine, 1-propyl di-(2-hexyl)phosphine, 1-propyl di-(3-hexyl)phosphine, 1-propyl di-(1-heptyl)phosphine, 1-propyl di-(2-heptyl)phosphine, 1-propyl di-(3-heptyl)phosphine, 1-propyl di-(4-heptyl)phosphine, 1-propyl di-(1-octyl)phosphine, 1-propyl di-(2-octyl)phosphine,1-Propyl di-(3-octyl)phosphine, 1-Propyl di-(4-octyl)phosphine, 1-Propyl di-(1-CH3(CH2)8)phosphine, 1-Propyl di-(2-CH3(CH2)8)phosphine, 1-Propyl di-(3-CH3(CH2)8)phosphine, 1-Propyl di-(4-CH3(CH2)8)phosphine, 1-Propyl di-(1-CH3(CH2)9)phosphine, 1-Propyl di-(2-CH3(CH2)9)phosphine, 1-Propyl di-(3-CH3(CH2)9)phosphine, 1-Propyl di-(4-CH3(CH2)9)phosphine, 1-Propyl di-(5-CH3(CH2)9)phosphine, 1-Propyl di-(1-CH3(CH2)10)phosphine, 1-Propyl di-(2-C H3(CH2)10)phosphine, 1-propyldi-(3-CH3(CH2)10)phosphine, 1-propyldi-(4-CH3(CH2)10)phosphine, 1-propyldi-(5-CH3(CH2)10)phosphine, 1-propyldi-(1-CH3(CH2)11)phosphine, 1-propyldi-(2-CH3(CH2)11)phosphine, 1-propyldi-(3-CH3(CH2)11)phosphine, 1-propyldi-(4-CH3(CH2)11)phosphine, 1-propyldi-(5-CH3(CH2)11)phosphine, 1-propyldi-(6-CH3(CH2)11)phosphine, 1-propyldi-(1-CH3(CH2)12)phosphine, 1-propyldi-(2-CH3(CH2)11)phosphine 2) Phosphine, 1-propyldi-(3-CH3(CH2)12)phosphine, 1-propyldi-(4-CH3(CH2)12)phosphine, 1-propyldi-(5-CH3(CH2)12)phosphine, 1-propyldi-(6-CH3(CH2)12)phosphine, 2-propyldi-(1-hexyl)phosphine, 2-propyldi-(2-hexyl)phosphine, 2-propyldi-(3-hexyl)phosphine, 2-propyldi-(1-heptyl)phosphine, 2-propyldi-(2-heptyl)phosphine, 2-propyldi-(3-heptyl)phosphine, 2-propyldi-(4-heptyl)phosphine, 2-propyldi-(1-octyl)phosphine, 2-propyldi-(2-octyl)phosphine, 2-propyldi-(3-octyl)phosphine, 2-propyldi-(4-octyl)phosphine, 2-propyldi-(4-octyl)phosphine, 2-propyl 2-propyl di-(1-CH3(CH2)8)phosphine, 2-propyl di-(2-CH3(CH2)8)phosphine, 2-propyl di-(3-CH3(CH2)8)phosphine, 2-propyl di-(4-CH3(CH2)8)phosphine, 2-propyl di-(1-CH3(CH2)9)phosphine, 2-propyl di-(CH3(CH2)9)phosphine, 2-propyl di-(3-CH3(CH2)9)phosphine, 2-propyl di-(4-CH3(CH2)9)phosphine, 2-propyl di-(5-CH3(CH2)9)phosphine, 2-propyl di-(1-CH3(CH2)10)phosphine, 2-propyl di-(2-CH3(CH2)10)phosphine, 2-propyl di-(3-CH3(CH2)10)phosphine,2-Propylbis-(4-CH3(CH2)10)phosphine, 2-Propylbis-(5-CH3(CH2)10)phosphine, 2-Propylbis-(1-CH3(CH2)11)phosphine, 2-Propylbis-(2-CH3(CH2)11)phosphine, 2-Propylbis-(3-CH3(CH2)11)phosphine, 2-Propylbis-(4-CH3(CH2)11)phosphine, 2-Propylbis-(5-CH3(CH2)11)phosphine, 2-Propylbis-(6-CH3(CH2)11)phosphine, 2-Propylbis-(1-CH3(CH2)12)phosphine, 2-Propylbis-(2-CH3(CH2)12)phosphine, 2-Propylbis-(3-CH3(CH2)12)phosphine, 2-Propylbis-( 4-CH3(CH2)12)phosphine, 2-propyldi-(5-CH3(CH2)12)phosphine, 2-propyldi-(6-CH3(CH2)12)phosphine, butyldi-(1-hexyl)phosphine, butyldi-(2-hexyl)phosphine, butyldi-(3-hexyl)phosphine, butyldi-(1-heptyl)phosphine, butyldi-(2-heptyl)phosphine, butyldi-(3-heptyl)phosphine, butyldi-(4-heptyl)phosphine, butyldi-(1-octyl)phosphine, butyldi-(2-octyl)phosphine, butyldi-(3-octyl)phosphine, butyldi-(4-octyl)phosphine, butyldi-(1-CH3(CH2)8)phosphine, butyldi-(2-CH3(CH2)8)phosphine, butyldi-(3-CH3(CH2)8)phosphine, butyl bis-(4-CH3(CH2)8)phosphine, butylbis-(1-CH3(CH2)9)phosphine, butylbis-(2-CH3(CH2)9)phosphine, butylbis-(3-CH3(CH2)9)phosphine, butylbis-(4-CH3(CH2)9)phosphine, butylbis-(5-CH3(CH2)9)phosphine, butylbis-(1-CH3(CH2)10)phosphine, butylbis-(2-CH3(CH2)10)phosphine, butylbis-(3-CH3(CH2)10)phosphine, butylbis-(4-CH3(CH2)10)phosphine, butylbis-(5-CH3(CH2)10)phosphine, butylbis-(1-CH3(CH2)11)phosphine, butylbis-(2-CH3(CH2)11)phosphine Phosphine, Butyldi-(3-CH3(CH2)11)phosphine, Butyldi-(4-CH3(CH2)11)phosphine, Butyldi-(5-CH3(CH2)11)phosphine, Butyldi-(6-CH3(CH2)11)phosphine, Butyldi-(1-CH3(CH2)12)phosphine, Butyldi-(2-CH3(CH2)12)phosphine, Butyldi-(3-CH3(CH2)12)phosphine, Butyldi-(4-CH3(CH2)12)phosphine, Butyldi-(5-CH3(CH2)12)phosphine, Butyldi-(6-CH3(CH2)12)phosphine, Methylhexylheptylphosphine, Methylhexyloctylphosphine, Ethylpropylbutylphosphine, Ethylpropylpentylphosphine, Ethylpropylhexylphosphine, Ethylpropylheptylphosphine,Ethylpropyl octylphosphine, ethylbutylpentylphosphine, ethylbutylhexylphosphine, ethylbutylheptylphosphine, ethylbutyloctylphosphine, ethylpentylhexylphosphine, ethylpentylheptylphosphine, ethylhexylheptylphosphine, ethylhexyloctylphosphine, tri-phenylphosphine, 1-hexyldi-phenylphosphine, 2-hexyldi-phenylphosphine, 3-hexyldi-phenylphosphine, 1-heptyldi-phenylphosphine, 2-heptyldi-phenylphosphine, 3-heptyldi-phenylphosphine, 1-heptyldi-phenylphosphine, 2-heptyldi-phenylphosphine, 3-heptyldi-phenylphosphine, 4-heptyldi-phenylphosphine, 1-octyldi-phenylphosphine, 2-octyldi-phenylphosphine, 3-octyldi-phenylphosphine, 4-octyldi-phenylphosphine, 1CH3(CH2)8-di-phenylphosphine, 2CH3(CH2)8-di-phenylphosphine, 3CH3(CH2)8-di-phenylphosphine, 4CH3(CH2)8-di-phenylphosphine 1CH3(CH2)9-di-phenylphosphine, 2CH3(CH2)9-di-phenylphosphine, 3CH3(CH2)9-di-phenylphosphine, 4CH3(CH2)9-di-phenylphosphine, 5CH3(CH2)9-di-phenylphosphine, 1CH3(CH2)10-di-phenylphosphine, 2CH3(CH2)10-di-phenylphosphine, 3CH3(CH2)10-di-phenylphosphine, 4CH3(CH2)10-di-phenylphosphine, 5CH3(CH2)10-di-phenylphosphine, 1CH3(CH2)11-di-phenylphosphine, 2CH3(CH2)11-di-phenylphosphine, 3CH3(CH2)11-di-phenylphosphine, 4CH3(CH2)11-di-phenylphosphine, 5CH3(CH2)11-di-phenylphosphine 6CH3(CH2)11 di-phenylphosphine, CH3(CH2)12 di-phenylphosphine, CH3(CH2)12 phenylphosphine, 3CH3(CH2)12 di-phenylphosphine, 4CH3(CH2)12 di-phenylphosphine, 5CH3(CH2)12 di-phenylphosphine, 6CH3(CH2)12 di-phenylphosphine, di-(1-hexyl)phenylphosphine, di-(2-hexyl)phenylphosphine, di-(3-hexyl)phenylphosphine, di-(1-heptyl)phenylphosphine, di-(2-heptyl)phenylphosphine, di-(3-heptyl)phenylphosphine, di-(4-heptyl)phenylphosphine, di-(1-octyl)phenylphosphine, di-(2-octyl)phenylphosphine, di-(3-octyl)phenylphosphine, di-(4-octyl)phenylphosphine, di- -(1-CH3(CH2)8)phenylphosphine, di-(2-CH3(CH2)8)phenylphosphine, di-(3-CH3(CH2)8)phenylphosphine, di-(4-CH3(CH2)8)phenylphosphine, di-(1-CH3(CH2)9)phenylphosphine, di-(2-CH3(CH2)9)phenylphosphine, di-(3-CH3(CH2)9)phenylphosphine, di-(4-CH3(CH2)9)phenylphosphine, di-(5-CH3(CH2)9)phenylphosphine, di-(1-CH3(CH2)10)phenylphosphine, di-(2-CH3(CH2)10)phenylphosphine, di-(3-CH3(CH2)10)phenylphosphine, di-(4-CH3(CH2)10)phenylphosphine,Bis-(5-CH3(CH2)10)phenylphosphine, Bis-(1-CH3(CH2)11)phenylphosphine, Bis-(2-CH3(CH2)11)phenylphosphine, Bis-(3-CH3(CH2)11)phenylphosphine, Bis-(4-CH3(CH2)11)phenylphosphine, Bis-(5-CH3(CH2)11)phenylphosphine, Bis-(6-CH3(CH2)11)phenylphosphine, Bis-(1-CH3(CH2)12)phenylphosphine, Bis-(2-CH3(CH2)12)phenylphosphine, Bis-(3-CH3(CH2)12)phenylphosphine, Bis-(4-CH3(CH2)12)phenylphosphine, bis-(5-CH3(CH2)12)phenylphosphine, bis-(6-CH3(CH2)12)phenylphosphine, tris-(phenylmethyl)phosphine, tris-(2-methylphenyl)phosphine, tris-(3-methylphenyl)phosphine, tris-(4-methylphenyl)phosphine, tris-(2-ethylphenyl)phosphine, tris-(3-ethylphenyl)phosphine, tris-(4-ethylphenyl)phosphine, tris-(hexene)phosphine, tris-(heptene)phosphine, tris-(octene)phosphine, tris-(heptyl)phosphine, tris-(heptyl)phosphine, tris-(heptyl)phosphine, and tris-(heptyl)phosphine.

[0075] Examples of phosphine oxides correspond to each of the phosphines listed above. A list of such oxides can be quickly generated by simply adding the word "oxidation" to each of the phosphine substances listed above.

[0076] Examples of diphosphonates include: tetra-methyl diphosphonate, tetra-ethyl diphosphonate, tetra-(1-propyl) diphosphonate, tetra-(2-propyl) diphosphonate, tetra-(1-butyl) diphosphonate, tetra-(2-butyl) diphosphonate, tetra-(1-tert-butyl) diphosphonate, tetra-(2-tert-butyl) diphosphonate, tetra-(1-pentyl) diphosphonate, tetra-(2-pentyl) diphosphonate, tetra-(3-pentyl) diphosphonate, tetra-(1-hexyl) diphosphonate, tetra-(2-hexyl) diphosphonate, tetra-(3-hexyl) diphosphonate, tetra-(1-heptyl) diphosphonate, tetra-(2-heptyl) diphosphonate, tetra-(1-(2-heptyl) diphosphonate, tetra-(1-(2-heptyl) diphosphonate, tetra-(1-(2-heptyl) diphosphonate) 3-Heptyl) ester, tetra-(4-heptyl) ester of di-phosphonate, tetra-(1-octyl) ester of di-phosphonate, tetra-(2-octyl) ester of di-phosphonate, tetra-(3-octyl) ester of di-phosphonate, tetra-(4-octyl) ester of di-phosphonate, tetra-(1-CH3(CH2)8) ester of di-phosphonate, tetra-(2-CH3(CH2)8) ester of di-phosphonate, tetra-(3-CH3(CH2)8) ester of di-phosphonate, tetra-(4-CH3(CH2)8) ester of di-phosphonate, tetra-(1-CH3(CH2)9) ester of di-phosphonate, tetra-(2-CH3(CH2)9) ester of di-phosphonate, tetra-(3-CH3(CH2)9) ester of di-phosphonate, tetra-(4-CH2)9) ester of di-phosphonate 3(CH2)9) ester, tetra-(5-CH3(CH2)9) ester, tetra-(1-CH3(CH2)10) ester, tetra-(2-CH3(CH2)10) ester, tetra-(3-CH3(CH2)10) ester, tetra-(4-CH3(CH2)10) ester, tetra-(5-CH3(CH2)10) ester, tetra-(1-CH3(CH2)11) ester, tetra-(2-CH3(CH2)11) ester, tetra-(3-CH3(CH2)11) ester, tetra-(4-CH3(CH2)11) ester, tetra-(4-CH3(CH2)11) ester, tetra- (5-CH3(CH2)11) ester, tetra-(6-CH3(CH2)12) ester, tetra-(3-CH3(CH2)12) ester, tetra-(2-CH3(CH2)12) ester, tetra-(3-CH3(CH2)12) ester, tetra-(4-CH3(CH2)12) ester, tetra-(5-CH3(CH2)12) ester, tetra-(6-CH3(CH2)12) ester, tetra-phenyl ester, di-methyl-(di-ethyl) ester, di-methyl-(di-phenyl) ester, and di-methyl-(di-4-pentene) ester.

[0077] Examples of pyrophosphate compounds include tetramethyl pyrophosphate, tetraethyl pyrophosphate, tetra-(1-propyl) pyrophosphate, tetra-(2-propyl) pyrophosphate, tetra-(1-butyl) pyrophosphate, tetra-(2-butyl) pyrophosphate, tetra-(1-tert-butyl) pyrophosphate, tetra-(2-tert-butyl) pyrophosphate, tetra-(1-pentyl) pyrophosphate, tetra-(2-pentyl) pyrophosphate, tetra-(3-pentyl) pyrophosphate, tetra-(1-hexyl) pyrophosphate, tetra-(2-hexyl) pyrophosphate, tetra-(3-hexyl) pyrophosphate, tetra-(1-heptyl) pyrophosphate, tetra-(2-heptyl) pyrophosphate, and tetra-(3-... Heptyl ester, tetra-(4-heptyl) ester, tetra-(1-octyl) ester, tetra-(2-octyl) ester, tetra-(3-octyl) ester, tetra-(4-octyl) ester, tetra-(1-CH3(CH2)8) ester, tetra-(2-CH3(CH2)8) ester, tetra-(3-CH3(CH2)8) ester, tetra-(4-CH3(CH2)8) ester, tetra-(3-CH3(CH2)9) ester, tetra-(2-CH3(CH2)9) ester, tetra-(3-CH3(CH2)9) ester, tetra-(4-CH3(CH2)9) ester, tetra-(4-CH3(CH2)9) ester CH2)9) ester, tetra-(5-CH3(CH2)9) ester, tetra-(4-CH3(CH2)10) ester, tetra-(2-CH3(CH2)10) ester, tetra-(3-CH3(CH2)10) ester, tetra-(4-CH3(CH2)10) ester, tetra-(5-CH3(CH2)10) ester, tetra-(4-CH3(CH2)11) ester, tetra-(2-CH3(CH2)10) ester, tetra-(3-CH3(CH2)11) ester, tetra-(4-CH3(CH2)11) ester, tetra- (5-CH3(CH2)11) ester, tetra-(6-CH3(CH2)11) ester, tetra-(5-CH3(CH2)12) ester, tetra-(2-CH3(CH2)12) ester, tetra-(3-CH3(CH2)12) ester, tetra-(4-CH3(CH2)12) ester, tetra-(5-CH3(CH2)12) ester, tetra-(6-CH3(CH2)12) ester, tetra-phenyl pyrophosphate, dimethyl-(di-ethyl) ester, dimethyl-(di-phenyl) ester, and dimethyl-(di-4-pentene) ester.

[0078] Other examples of phosphorus-containing compounds include those described in A. Toy and E. Walsh's "Phosphorus Chemistry in Everyday Living" (2nd edition, 1987, ACS, Washington, DC). Examples include:

[0079] Pyrophosphates, phosphonites, thiophosphates, thiophosphonates, phosphonates, dithiophosphates, bis-dithiophosphates, dithiophosphonates, thiophosphoramide esters, and pyrophosphoramides. Specific substances include: tetra-propyl dithiophosphate, tetra-ethyl dithiophosphate, O-ethyl-O-[2-(di-isopropylamino)ethyl] methylphosphonic acid, O,O-dimethyl-Op-nitrophenyl phosphate, O,O-diethyl-Op-nitrophenyl phosphate, O,O-dimethyl-O-(4-nitro-m-tolyl) phosphate, O-ethyl-Op-nitrophenyl phenyl thiophosphonic acid, O,O-diethyl-O-(3,5,6-trichloro-2-pyridyl) phosphate, O,O-diethyl-O-(2-isopropyl-6-methyl-4-pyrimidinyl) phosphate, and O,O-diethyl-O-[4-methylsulfinyl)phenyl] phosphate (O,O-diethyl) O-[4-methylsulfmyl)phenyl]phosphorothioate, O,O-dimethyl O-[3-methyl-4-(methylthio)phenyl] ester of thiophosphate, O,O-dimethyl ester of (2,2,2-trichloro-1-hydroxy-ethyl)phosphonic acid, 2,2-di-chlorovinyl dimethyl phosphate, 1,2-di-bromo-2,2-di-chloroethyl dimethyl phosphate, 2-chloro-1-(2,3,4-trichloro-phenyl) phosphate (1,1-Dimethyl-ethyl)-vinyl dimethyl ester, O-(4-bromo-2-chloro-phenyl)-O-ethyl-S-propyl ester of dithiophosphate, O-ethyl-O-[4-(methyl-thio)phenyl]-S-propyl ester of dithiophosphate, O-ethyl-S,S-di-propyl ester of dithiophosphate, diethyl mercapto-succinate, S-esters containing O,O-dimethyl dithiophosphate, S-[(1,1-dimethyl-ethyl)-thio)methyl]O,O-diethyl ester of dithiophosphate, O,O-di-di-dithiophosphate Methyl S-phthalimide-methyl ester, dithiophosphate O,O-dimethyl S-4-oxylidene-1,2,3-benzotriazine 3(4H)-methyl ester, bis-dithiophosphate O,O,O',O”-tetraethyl S,S'-methylene ester, dithiophosphate S-[(6-chloro-2-oxylidene-3-(2H)-benzoxazolyl)methyl]O,O-di-ethyl ester, dithiophosphate S-[(p-chlorophenyl-thio)methyl]O,O-diethyl ester, dithiophosphate 1,4-p-dioxane-2,3,-di-thio-S,S-bis(O,O-diethyl ester), ethyl dithiophosphonic acid O-ethyl S-phenyl ester, thiophosphoramide O,S-dimethyl ester, acetyl-thiophosphoramide O,S-dimethyl ester, 2-[[ethoxy[(1-methylethyl)amino]thiophosphonyl]oxy]benzoic acid 1-methylethyl ester, dimethyl dichlorovinyl phosphate, dithiophosphonic acid O,O-diethyl S-ethyl-thiomethyl ester, dithiophosphonic acid O,O-dimethyl S-(methyl-carbamoylmethyl) ester, (1-methylethyl)-phosphatidylethyl 3-methyl-4-(methylthio)phenyl ester, O,O-dimethyl O-[2-(methylcarbamoyl)-1-methyl-vinyl] ester, and octamethyl pyrophosphoramide.

[0080] Specific examples of phosphonates include: ethyl pentyl phosphonate, ethyl hexyl phosphonate, ethyl heptyl phosphonate, ethyl octyl phosphonate, ethyl decyl phosphonate, ethyl phenyl phosphonate, butyl pentyl phosphonate, butyl hexyl phosphonate, butyl heptyl phosphonate, pentyl dibutyl phosphonate, hexyl dibutyl phosphonate, and heptyl dibutyl phosphonate.

[0081] Examples of phosphonic acids include: pentylphosphonic acid, hexylphosphonic acid, heptylphosphonic acid, octylphosphonic acid, decylphosphonic acid, phenylphosphonic acid, dipentylphosphonic acid, diheptylphosphonic acid, didecylphosphonic acid, diphenylphosphonic acid, phenylhexylphosphonic acid, and pentyldecylphosphonic acid.

[0082] Examples of phosphinous acids include: monopentyl phosphinous acid, monohexyl phosphinous acid, monoheptyl phosphinous acid, monooctyl phosphinous acid, monodecyl phosphinous acid, monophenyl phosphinous acid, dipropyl phosphinous acid, dipentyl phosphinous acid, diheptyl phosphinous acid, didecyl phosphinous acid, diphenyl phosphinous acid, and propyldecyl phosphinous acid.

[0083] Examples of phosphonates include: hexyl pentyl phosphonate, heptayl pentyl phosphonate, octyl pentyl phosphonate, decyl pentyl phosphonate, phenyl pentyl phosphonate, dibutyl pentyl phosphonate, dihexyl phosphonate, heptayl phosphonate, pentyl phosphonate, octyl phosphonate, and phenyl phosphonate.

[0084] Examples of phosphonic acids include: pentylphosphonic acid, hexylphosphonic acid, heptylphosphonic acid, octylphosphonic acid, decylphosphonic acid, phenylphosphonic acid, methylpentylphosphonic acid, methylphenylphosphonic acid, pentylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, and pentyloctylphosphonic acid.

[0085] Examples of phosphonites include: ethyl pentyl phosphonite, ethyl hexyl phosphonite, ethyl heptyl phosphonite, ethyl octyl phosphonite, ethyl decyl phosphonite, ethyl phenyl phosphonite, butyl pentyl phosphonite, butyl hexyl phosphonite, butyl heptyl phosphonite, diethyl pentyl phosphonite, diethyl hexyl phosphonite, and diethyl heptyl phosphonite.

[0086] Examples of phosphonites include: 1-pentylphosphonites, 2-pentylphosphonites, 3-pentylphosphonites, 1-hexylphosphonites, 2-hexylphosphonites, 3-hexylphosphonites, 1-heptylphosphonites, 2-heptylphosphonites, 3-heptylphosphonites, 4-heptylphosphonites, octylphosphonites, decylphosphonites, and phenylphosphonites.

[0087] A complex is formed between a phosphorus-containing compound and an acyl halide before or during the reaction between the acyl halide and the amine. The phosphorus-containing compound can be added directly to the acyl halide solution before the acyl halide and amine solution are brought into contact, thus allowing sufficient opportunity for the complex to form before the reaction between the amine and the acyl halide.

[0088] Suitable co-solvents can be selected from solvents having the general formula R1-O-R2, silanes, and aromatic compounds. Substituent R1 can be selected from the group consisting of straight-chain or branched C1-C6 lower alkyl, C1-C6 lower alkenyl, or C1-C6 lower alkynyl groups, optionally substituted by 1 to 3 substituents selected from the following groups: methyl, ethyl, propyl, fluorine, chlorine, bromine, iodine, hydroxyl, aldehyde, carboxylic acid, amine, amide, nitrile, methoxy, ethoxy, propoxy, isopropoxy, and any combination thereof. In particular, R1 can be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, sec-isopentyl, n-hexyl, isohexyl, 3-methylpentyl, neohexyl, and 2,3-dimethylbutyl.

[0089] Substituent R2 may be selected from the group consisting of: straight-chain or branched C1-C6 lower alkyl, C1-C6 lower alkenyl, C1-C6 lower alkynyl, carbonyl C1-C6 lower alkyl, carbonyl C1-C6 lower alkenyl, carbonyl C1-C6 lower alkynyl, optionally substituted by 1 to 3 substituents selected from the group consisting of: methyl, ethyl or propyl, fluorine, chlorine, bromine, iodine, hydroxyl, aldehyde, carboxylic acid, amine, amide, nitrile, methoxy, ethoxy, propoxy, isopropoxy and any combination thereof. Specifically, R2 may be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, sec-isopentyl, n-hexyl, isohexyl, 3-methylpentyl, neohexyl, 2,3-dimethylbutyl, formyl, acetyl, propionyl, n-butyryl, isobutyryl, n-valeryl, isovaleryl, sec-valeryl, tert-valeryl, n-hexanoyl, isohexanoyl, sec-hexanoyl, 3-methylvaleryl, neohexanoyl, and 2,3-dimethylbutyryl.

[0090] Preferred co-solvents include ethyl acetate, diethyl ether, and ethyl formate.

[0091] Other suitable co-solvents include silanes and aromatic compounds. Silanes can be selected from those having the general formula X3-Si-R. 1The group of compounds, wherein X is a halogen independently selected from the group consisting of F, Cl, Br and I, and R 1 As defined above. Aromatic compounds typically comprise an aromatic ring structure, including an aromatic heterocyclic structure. In embodiments, the aromatic compound comprises a benzene ring optionally substituted with 1 to 5 substituents selected from the group consisting of: methyl, ethyl, propyl, fluorine, chlorine, bromine, iodine, hydroxyl, aldehyde, carboxylic acid, amine, amide, nitrile, methoxy, ethoxy, propoxy, isopropoxy, and any combination thereof.

[0092] Appropriately, the cosolvent is not an alkane, such as a C5-C12 alkane.

[0093] The primary solvent for the organic phase can be selected from a large group of compounds. Suitable organic solvents are one or more of the following nonpolar solvents (such as hydrocarbons), which may be unsubstituted or substituted. Nonpolar solvents include aromatic hydrocarbons, such as monoalkyl-substituted or polyalkyl-substituted benzenes, such as toluene, xylene, mesitylene, ethylbenzene, or monoalkyl-substituted or polyalkyl-substituted naphthalenes, such as 1-methylnaphthalene, 2-methylnaphthalene, or dimethylnaphthalene, or other benzene-derived aromatic hydrocarbons, such as indane or tetrahydronaphthalene or mixtures thereof. Nonpolar solvents also include aliphatic hydrocarbons, such as those of formula C n H 2n+2 Straight-chain aliphatic compounds, wherein n = 5-12, or branched aliphatic compounds. Suitable examples of straight-chain or branched aliphatic compounds include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, 2-methylbutane (isopentane), 2,2,4-trimethylpentane (isooctane), isohexane, isoheptane, isononane, isododecane, isoundecane, isododecane, or combinations thereof. Nonpolar aliphatic solvents also include cyclic, optionally alkyl-substituted aliphatic compounds, such as cyclohexane or methylcyclopentane; or mixtures thereof. Nonpolar aliphatic solvents as D series series or This series is commercially available. Preferred nonpolar aliphatic solvents include... E has a distillation range of 115-140℃ and an aromatic content of less than 0.002% by weight. E mainly includes C7 to C10 alkanes. Another suitable nonpolar aliphatic solvent is C has a distillation range of 99-104℃ and an aromatic content of less than 0.001.

[0094] Other organic solvents considered include mixtures of aromatic and aliphatic hydrocarbons, such as... A series of solvents, for example, 100 150 or 200 (ExxonMobil Chemicals); A series of solvents (TotalFinaElf); or Series, for example, 28 (Petrochem Carless).

[0095] After reacting an aqueous phase polyfunctional amine monomer with an organic phase polyfunctional acyl halide monomer to form a crosslinked polyamide thin composite layer on a support membrane, the solvent and co-solvent are typically removed from the crosslinked polyamide layer by dissolution, rinsing, or washing. In one embodiment, the solvent and co-solvent are removed by maintaining the semipermeable membrane in a bath for a certain period of time and then drying the semipermeable membrane.

[0096] While the membrane is expected to be used for any of the aforementioned semipermeable membranes and to facilitate forward osmosis, water flux typically becomes more efficient when aquaporin water channels are introduced into the TFC layer. Aquaporin water channels are widely distributed transmembrane proteins in nature, used to selectively transport water into or out of cells. In industrial environments, aquaporin water channels in semipermeable membranes ensure water flow through osmosis, while other solutes in the solution are retained. Therefore, the presence of active aquaporin water channels helps the semipermeable membrane retain solutes and facilitates water permeation through the membrane.

[0097] Aquaporin water channels are introduced into membranes with an active structure for at least a significant amount of molecules. According to aspects of the invention, the activity of aquaporin water channels is maintained when they are assembled in nanostructures comprising polyalkylene imides (such as polyethyleneimine). As further explained in detail in WO17137361 (which is incorporated herein by reference in its entirety), polyalkylene imides, such as polyethyleneimine (PEI), form self-assembled nanostructures with transmembrane proteins, such as aquaporin water channels. The nanostructures ensure that at least a portion of the aquaporin water channels remain active even after introduction into a TFC layer. It is believed that the polymer interacts with the transmembrane protein to prevent it from reacting with monomers involved in the formation of the TFC layer. Furthermore, it is believed that the PEI of the aquaporin nanoparticles reacts with the PAI and thus becomes integrated into the transition layer.

[0098] Generally, PEIs are essentially straight-chain or branched polymers with average molecular weights ranging from about 2,000 Da to about 10,000 Da, such as about 3,000 Da to about 5,000 Da. It is currently believed that the relatively short polymers interact with transmembrane proteins to prevent them from reacting with monomers involved in TFC layer formation, while at the same time they do not substantially inhibit interactions with water.

[0099] To prevent the aggregation of aquaporin water channels, it can be advantageous to dissolve the aquaporin water channels in a cleaning agent before assembly into nanostructures comprising polyalkylimides. Since aquaporin water channels are naturally present in cell membranes, the protein exhibits hydrophobic domains. It is believed that the hydrophobic domains of the cleaning agent interact with the hydrophobic domains of the aquaporin water channels, thereby forming dissolved proteins. Although aquaporin water channels can be dissolved by a variety of cleaning agents, those selected from the group consisting of LDAO, OG, DDM, or combinations thereof are currently preferred.

[0100] In another embodiment of the invention, the aquaporin water channels are provided in vesicles prior to the introduction of the TFC layer. Vesicles are the natural environment of the aquaporin water channels, and vesicles can be formed from many different membrane-forming materials, including naturally occurring phospholipids. In one embodiment of the invention, vesicles are formed from amphiphilic diblock copolymers, such as poly(2-methyloxazoline)-block-poly(dimethylsiloxane) diblock copolymers (PMOXA-PDMS) and reactive end-functionalized poly(dimethylsiloxane) (PDMS).

[0101] The two blocks of the PMOXA-PDMS diblock copolymer can have different lengths. To obtain sufficient stability of the vesicles, the PMOXA-PDMS diblock copolymer is typically selected from the group consisting of PMOXA10-40-PDMS25-70 and mixtures thereof. Experiments have shown that mixtures of different PMOXA-PDMS diblock copolymers exhibit higher robustness. In a preferred embodiment, the vesicles therefore comprise at least a first amphiphilic diblock copolymer of the general formula PMOXA10-28-PDMS25-70 and a second amphiphilic diblock copolymer of the general formula PMOXA28-40-PDMS25-70. The weight ratio between the first and second amphiphilic diblock copolymers is typically in the range of 0.1:1 to 1:0.1. The concentration of the amphiphilic diblock copolymer in the liquid composition is generally in the range of 0.1 to 50 mg / ml, such as 0.5 to 20 mg / ml, and preferably 1 to 10 mg / ml.

[0102] The reactively terminal-functionalized PDMS (reactively terminal-functionalized poly(dimethylsiloxane)) of the vesicle can be functionalized with one or more of amine, carboxylic acid, and / or hydroxyl groups. In one aspect of the invention, the reactively terminal-functionalized PDMSe-f is a bis(aminoalkyl), bis(hydroxyalkyl), or bis(carboxylic alkyl)-terminated PDMSe-f, such as poly(dimethylsiloxane), bis(3-aminopropyl), or poly(dimethylsiloxane), bis(3-hydroxypropyl). Suitably, the integer e is selected from the range of 20 to 40, such as 30, and the integer f is selected from the range of 40 to 80, such as 50. Furthermore, the reactively terminal-functionalized PDMSe-f can be selected from the group consisting of H2N-PDMS30-50, HOOC-PDMS30-50, and HO-PDMS30-50 and mixtures thereof. Before the vesicles are introduced into the aquaporin water channels, the vesicles may be present in the liquid composition, and the amount of PDMS is preferably from about 0.05% to about 1% v / v.

[0103] The vesicles of the present invention may further comprise about 1% v / v to about 12% v / v of a PMOXAa-b-PDMSc-d-PMOXAa-b type triblock copolymer to increase their integrity. Typically, the vesicles comprise about 8% v / v to about 12% v / v of a PMOXAa-b-PDMSc-d-PMOXAa-b type triblock copolymer. The PMOXAa-b-PDMSc-d-PMOXAa-b type triblock copolymer is typically selected from PMOXA10-20-PDMS25-70-PMOXA10-20.

[0104] The vesicles of the present invention may further include flux enhancers to increase water flux or reduce reverse salt flux. Flux enhancers may be selected from a large group of compounds, typically preferably alkylene glycol monoalkyl ether alkylates, β-cyclodextrins, or polyethylene glycol (15)-hydroxystearate. The flux enhancer is typically present in an amount of 0.1% to 1% by weight of the liquid composition.

[0105] The vesicles of the present invention may be present in a liquid composition prior to being immobilized in a membrane (such as a TFC layer provided on a support membrane). The liquid composition may include a buffer to stabilize the vesicles. The transmembrane protein is appropriately dissolved in a cleaning agent before being mixed with other components. The vesicles in the liquid composition may further include a cleaning agent or a surfactant. The cleaning agent may be selected from the group consisting of lauryl dimethylamine N-oxide (LDAO), octyl glucoside (OG), dodecyl maltodextrin (DDM), or combinations thereof.

[0106] Without being bound by any particular theory, it is believed that vesicles containing free, available reactive groups on the surface will not only be physically introduced or immobilized (adsorbed) but also chemically bonded to the TFC layer, as reactive free end groups such as amino, hydroxy, and carboxyl groups will participate in interfacial polymerization reactions with acyl chlorides such as trimesoyl chloride (TMC). In this way, vesicles are believed to be covalently bound to the TFC layer, resulting in a relatively high vesicle loading and therefore a higher water flux through the membrane. Furthermore, it is currently believed that free end groups, such as amino or hydroxyl groups, can react with the carbonyl groups of PAI to form covalent bonds between the vesicles and the supporting hollow fiber membrane. Moreover, it is believed that when introduced into selective membrane layers, the covalent coupling of vesicles in the TFC layer leads to greater stability and / or lifetime of aquaporin water channels and vesicles containing aquaporin water channels.

[0107] Vesicles can be prepared in a liquid composition incorporating aquaporin water channels, comprising the steps of stirring a solution of a PMOXAa-b-PDMSc-d type amphiphilic diblock copolymer, 0.05% to about 1% of a mixture of reactive end-functionalized PDMSe-f and aquaporin water channels. For best results, stirring should be continued for 12-16 hours.

[0108] The preparation of a thin-film composite layer immobilizing vesicles introducing aquaporin water channels on a porous basement membrane comprises the following steps: providing a mixture of vesicles and a diamine or triamine compound in a liquid composition as disclosed above; covering the surface of a porous support membrane with the mixture; applying a hydrophobic solution comprising an acyl halide compound; and allowing the aqueous solution and the hydrophobic solution to undergo an interfacial polymerization reaction to form the thin-film composite layer. In one embodiment of the invention, the hydrophobic solution further comprises 0.1 to 10% by volume of a TFC layer modifier. The purpose of the TFC layer modifier is to increase water flow and / or solute retention. In suitable embodiments, the TFC layer modifier is a C3 to C8 carbonyl compound. As an example, the TFC layer modifier is selected from the group consisting of: diethylidene ketone, 2-pentanone, 5-pentanone, and / or cyclopentanone.

[0109] Porous support membranes can be hollow fiber membranes or flat sheet membranes. Currently, flat sheet membranes are suitable for and can be used to produce various components, such as plate and frame components or spiral wound components.

[0110] For the purposes of this document, the term "semi-permeable membrane" includes selectively permeable membranes and semi-permeable membranes used for water filtration and separation, such as asymmetric membranes, which include a porous support membrane with a selective layer formed on one side, such as a thin cross-linked aromatic polyamide layer or the other side may be reinforced by a woven or non-woven layer or mesh, typically made of polyester fibers.

[0111] Furthermore, the semi-permeable membrane of the present invention can be used in methods for concentrating product solutions, the methods including using the separation membrane of the present invention installed in a filter housing or assembly to extract water from the product solution, for example by forward osmosis.

[0112] In one aspect of the invention, it includes a hollow fiber (HF) assembly having a membrane of hollow fiber bundles modified with the selective layer of the invention. Preferably, the selective layer comprises a thin film composite (TFC) layer formed on the inner surface of the fiber by an interfacial polymerization reaction.

[0113] The separation membrane of the present invention can also be used in a method for generating salinity energy by using pressure to delay osmosis, the method comprising using the separation membrane to increase hydrostatic pressure and using the increase in hydrostatic pressure as a source of salinity energy, see WO2007 / 033675 and WO 2014128293(A1).

[0114] As used herein, the term "aquaporin" includes functional natural or synthetic aquaporins or aquaglycerol channel proteins, such as aquaporin Z (AqpZ), GluPf, SoPIP2;1, aquaporin 1, and / or aquaporin 2. Aquaporin channels include bacterial and eukaryotic aquaporins, such as yeast aquaporins, plant aquaporins, and mammalian aquaporins, as well as related channel proteins, such as aquaglycerol channel proteins. Examples of aquaporins and water-glycerol channel proteins include: prokaryotic aquaporins, such as AqpZ; mammalian aquaporins, such as Aqp1 and Aqp2; plant aquaporins, such as plasma membrane intrinsic proteins (PIPs), vacuole membrane intrinsic proteins (TIPs), nodulin intrinsic proteins (NIPs), and small intrinsic proteins (SIPs), such as SoPIP2;1, PttPIP2;5, and PtPIP2;2; yeast aquaporins, such as AQY1 and AQY2; and water-glycerol channel proteins, such as GlpF and Yfl054. Aquaporins (water channel proteins) can be prepared according to the methods described herein or as listed in Karlsson et al. (FEBS Letters 537:68-72, 2003) or as described in Jensen et al. US 2012 / 0080377 A1 (see, for example, Example 6).

[0115] Examples of semi-permeable membranes are nanofiltration (NF) membranes, forward osmosis (FO) membranes, and reverse osmosis (RO) membranes. Flat-sheet TFC membranes are typically fabricated by depositing a polyamide layer on top of a porous layer of polyethersulfone or polysulfone on top of a nonwoven or woven fabric support. The polyamide repellent layer is formed by interfacial polymerization of an aqueous solution of an amine with a solution of an acyl chloride in an organic solvent. TFC membranes can be produced as described in WO 2013 / 043118 (Nanyang Technological University & Aquaporin A / S).

[0116] The “thin film composite” or (TFC) membrane used herein can be prepared using polyfunctional amine reactants in aqueous solutions, preferably aromatic amines, such as diamines or triamines, for example 1,3-diaminobenzene (m-phenylenediamine, purity >99%, available from Sigma-Aldrich), and polyfunctional acyl halide reactants dissolved in organic solvents, such as diacyl chlorides or triacyl chlorides, preferably aromatic acyl halides, for example benzene-1,3,5-tricarbonyl chloride (CAS No. 84270-84-8, trimesoyl chloride (TMC), available from Sigma-Aldrich), wherein the reactants are combined in an interfacial polycondensation reaction, see Khorshidi et al. (2016) Scientific Reports 6, Article number: 22069 and U.S. Patent No. 4,277,344, which describe in detail the formation of a composite membrane comprising a polyamide laminated on a porous membrane support (e.g., a polyethersulfone membrane) on the surface of a porous membrane support (e.g., a polyethersulfone membrane).

[0117] Forward osmosis (FO), or direct osmosis, is a osmotic process that uses a selective and permeable membrane to separate water from dissolved solutes. The driving force for this separation is the osmotic pressure gradient between a high-concentration solution (referred to herein as the draw) and a low-concentration solution (referred to herein as the feed). This osmotic pressure gradient causes a stream of purified water to flow through the membrane into the draw, effectively concentrating the feed. The draw solution can consist of a single or multiple simple salts, or it can be a substance specifically tailored for forward osmosis applications. The feed solution can be a diluted product stream, such as a beverage, waste stream, or seawater.

[0118] Therefore, most applications of forward osmosis (FO) fall into three main categories: product concentration, waste concentration, or producing clean water as a byproduct of the concentration process. Membranes can be used in all types of forward osmosis processes and can be specifically adapted to each type.

[0119] As used herein, the term “reverse osmosis” (RO) refers to the process where the feed water pressure applied to a selectively osmotic membrane is used to overcome osmotic pressure. Reverse osmosis typically removes many types of dissolved and suspended matter, including bacteria, from feed water and is used in both industrial processes and for the production of drinking water. During the RO process, the solute remains on the pressurized side of the membrane, and the pure solvent (permeate) passes through to the other side. Selectivity specifies that the membrane does not allow larger molecules or ions to pass through its pores (holes), while allowing smaller components of the solution, such as solvent molecules, to pass freely. Low-pressure reverse osmosis (LPRO) membranes are typically operated at specific flow rates from feed water pressures of about <5 bar to a maximum operating pressure of about 25 bar, at a range of 15 LMH / bar. LPRO operates at lower feed pressures, such as 2 to 5 bar, and is sometimes specified as ultra-low pressure reverse osmosis. LPRO membranes known in the art have typical operating limitations for feed water temperatures of about 45°C, feed water pH in the range of 2 to 11, and chemical cleaning in the range of pH 1 to 12.

[0120] The invention is further illustrated by referring to the following non-limiting embodiments.

[0121] Example

[0122] 1.1： Production of support membrane

[0123] The coating was prepared by dissolving 17% polysulfone (Solvay P3500 MB7 LCD) in 83% DMF (N,N-dimethylformamide) obtained from TACT Chemie. The coating was mixed in a sealed container at 45°C for 8 hours at a mixing speed of 90 rpm to obtain a uniform viscosity.

[0124] Using a casting gap of 230 μm, the coating was cast onto a nonwoven polyester sheet (model PMB-SKC) obtained from Mitsubishi using a knife-over-roll casting method. After an exposure time of 1.9 s, phase inversion was achieved by quenching in water at 13 °C for 16 s. Subsequently, the support film was washed in water at 60 °C for 120 s. A thickness of approximately 130 μm was obtained.

[0125] 1.2： Production of water channels protein water channels

[0126] Expression of histidine-tagged aquaporins from japonica rice (Oryza sativa Japonica) in Escherichia coli and their purification using immobilized metal affinity chromatography (IMAC)

[0127] The gene encoding an aquaporin from japonica rice (UNIPROT: A3C132) was codon-optimized using Geneart (a subsidiary of Thermo Fischer Scientific) services to improve expression in *E. coli*. The resulting gene (gene ID: aquaporin_Oryza_sativa_Japonica) was synthesized by adding a ten-histidine codon to the C-terminus and flanking NdeI / XhoI restriction sites at both the N-terminus and C-terminus. The synthesized gene fragment was digested with NdeI / XhoI restriction enzymes and ligated into the NdeI / XhoI-digested and purified vector pUP1909 fragment. The resulting ligation mixture was transformed into *E. coli* DH10B, and kanamycin-resistant transformants were selected on LB agar plates containing kanamycin. Transformants were confirmed by sequencing of the genetic construct. The isolated vector DNA was then transferred to the production host *E. coli* BL21.

[0128] To heterologously express aquaporins in *E. coli*, the production host was grown in a basic culture medium consisting of: 30 g / L glycerol, 6 g / L (NH4)2HPO4, 3 g / L KH2PO4, 5 g / L NaCl, 0.25 g / L MgSO4·7H2O, 0.4 g / L Fe(III) citrate, and 1 mL / L sterile filtered trace metal solution. The trace metal solution consisted of: 1 g / L EDTA, 0.8 g / L CoCl2·6H2O, 1.5 g / L MnCl2·4H2O, 0.4 g / L CuCl2·2H2O, 0.4 g / L H3BO3, 0.8 g / L Na2MoO4·2H2O, and 1.3 g / L Zn(CH3COO)2·2H2O. After inoculation and overnight growth, an additional 0.25 g / L MgSO4·7H2O was added.

[0129] Escherichia coli was cultured in a 3L Applikon bioreactor equipped with ez-Control during batch fermentation. Protein production was induced by adding IPTG to a final concentration of 0.5 mM at an optical density of approximately 30 (OD 600 nm). The culture was induced for approximately 24 hours and bacterial cells were harvested by centrifugation at 5300 g for 20 min.

[0130] The pellet containing E. coli cells was resuspended in buffer (an aqueous solution of protease inhibitors PMSF and EDTA) and homogenized at 1000 bar in a Stansted nm-GEN 7575 homogenizer. The temperature was maintained at approximately 10–15 °C. The mixture was centrifuged at a maximum speed of 5300 g for 30 minutes. The pellet contained membrane proteins, and the supernatant was discarded.

[0131] The precipitate was resuspended in 0.9% sodium chloride solution to obtain a total protein concentration of approximately 50 mg / ml. Membrane proteins were dissolved by adding 28 L LTRIS binding buffer and 4.5 L 5% n-lauryl dimethylamine N-oxide (LDAO) to 5 L of the resuspended precipitate. The mixture was incubated at room temperature with gentle stirring for 2 to 24 hours.

[0132] After the dissolution process, the mixture was centrifuged at 5300g for 90 minutes in a 2L container. The supernatant was recovered and the LDAO concentration was adjusted to 0.2% by adding dilution buffer.

[0133] After dissolution and clarification, the protein was captured using IMAC and eluted in an elution buffer containing 1000 mM imidazole and 0.2% w / v LDAO. The eluted fraction was analyzed by SDS-PAGE and showed only a single major band migrating at 27 kDa, corresponding to the size of an aquaporin derived from Japanese rice. This result was further confirmed by comparison with a negative control purification from *E. coli* transformed with an empty vector. The negative control resulted in no purified protein. Western blot analysis using a histidine tag-specific antibody (TaKaRa Bio) yielded, as expected, a clear signal from the purified protein and no signal from the negative control, confirming the purified protein as a histidine-tagged membrane protein.

[0134] A stock solution was prepared by adjusting the protein concentration to 5 mg / ml with ice-cold imidazole-free buffer containing 2% LDAO. Finally, the aquaporin stock solution was sterilized by filtration through a 0.45 μM sterile cup and stored at 4°C for use within one month, or at -80°C in a freezer.

[0135] 1.3 Production of aquaporin preparations

[0136] 1. A 0.5% KHS solution was prepared by dissolving 5g KHS in 1L PBS (prepared by dissolving 8g NaCl, 0.2g KCl, 1.44g Na2HPO4 and 0.24g KH2PO4 in 800mL MiliQ purified H2O, adjusting the pH to 7.2 with HCl, and bringing the volume to 1L). HS 15 (polyethylene glycol (15)-hydroxystearate) (KHS) solution.

[0137] 2. Prepare a 0.05% LDAO solution in PBS by dissolving 0.05g LDAO in 100mL PBS.

[0138] 3. In the preparation container, weigh 0.5g of poly(2-methyloxazoline)-block-poly(dimethylsiloxane) diblock copolymer (PDMS). 65 PMOXA 24 The formulation was prepared at ) / L.

[0139] 4. In the same preparation container, weigh out the poly(2-methyloxazoline)-block-poly(dimethylsiloxane) diblock copolymer (PDMS). 65 PMOXA 32 ), to achieve a formulation prepared with 0.5 g / L (PDMS) 65 PMOXA 24 and PDMS 65 PMOXA 32 The concentration is 1:1 (by weight).

[0140] 5. In the same preparation container, add poly(2-methyloxazoline)-block-poly(dimethylsiloxane)-block-poly-(2-methyloxazoline) triblock copolymer PMOXA 12 PDMS 65 PMOXA 12 To achieve a concentration of 0.12 g / L in the prepared formulation.

[0141] 6. Add 0.05% of the LDAO prepared in step 2 at a ratio of 100 mL / L of the prepared formulation.

[0142] 7. Add bis(3-aminopropyl)-terminated poly(dimethylsiloxane) with a molecular weight of 2500 Da to achieve a final concentration of 0.1%.

[0143] 8. Add aquaporin stock solution to achieve a concentration of 5 mg / L for the prepared formulation and a protein:polymer ratio of 1 / 400.

[0144] 9. Add 3% by weight of the KHS solution prepared in step 1 to achieve the required volume of the prepared formulation minus the volume of LDAO, bis(3-aminopropyl)-terminated poly(dimethylsiloxane), and aquaporin added in steps 6 and 8.

[0145] 10. Stir the mixture from step 9 at 170 rpm overnight (no more than 20 hours) at room temperature to obtain the formulation.

[0146] 11. The next morning, take the preparation obtained in the order of steps 1 to 10, sterilize it by filtering it through a 200 nm pore size filter, put it into a sealed bottle and store it at room temperature for no more than 12 months.

[0147] 1.4： TFC layer on production support membrane

[0148] a. Prepare an aqueous solution by mixing the following in DI water:

[0149] i. 2.5% MPD

[0150] ii. 2.5% ε-caprolactam (CAP)

[0151] iii. 5% aquaporin preparation

[0152] b. Prepare an organic solution by mixing the following in Isopar E:

[0153] i. 0.15% TMC

[0154] ii. 0% or 1.25% Tributyl Phosphate (TBP)

[0155] iii.0%, 0.5%, 1.0% or 2.0% co-solvent

[0156] c. TFC formation

[0157] i. Immerse the support membrane in an aqueous solution for 30 seconds.

[0158] ii. Dry the membrane using an air gun at 1 bar.

[0159] iii. Add organic solvent for 30 seconds.

[0160] iv. Dry the membrane using an air gun at approximately 0.5 bar.

[0161] d. Place the membrane with the TFC layer in 15% citric acid at 70°C for 4 min, and then in RO water at 70°C for 2 min.

[0162] 1.5： result

[0163] Table 1: Ethyl acetate

[0164]

[0165] Table 2: Diethyl ether

[0166]

[0167]

[0168] Table 3: Ethyl formate

[0169]

[0170] The results showed that adding cosolvent or TBP at concentrations of 0.5% and 1.25% significantly increased the flux from 3.2 LMH / bar to 5.6–6.1 LMH / bar. However, when the cosolvent and TBP were used at the same concentration, the combined effect increased to 6.8–7.2 LMH / bar. The results also showed that the flux could be further increased by adding more cosolvent to the mixture. Therefore, when the cosolvent concentration increased to 1.0% and the TBP concentration remained at 1.25%, the flux increased for all tested cosolvents, with flux values ​​ranging from 7.1–7.8 LMH / bar.

[0171] Example 2

[0172] The experiments reported in Example 1 were repeated; however, (3,3,3-trifluoropropyl)trichlorosilane (TFPTCS) was chosen as the co-solvent, and the amount of TMC was adjusted according to the amount of TBP. The results are shown in Table 4 below:

[0173] Table 4:TFPTCS

[0174]

[0175] The results showed that adding TFPTCS to an organic phase that already contained TBP enhanced the effect in a concentration-dependent manner.

[0176] Example 3

[0177] The experiments reported in Example 1 were repeated; however, mesitylene was chosen as the co-solvent. As shown in Example 1.4 above, the amount of TMC was 0.15%. The results are shown in Table 5 below:

[0178] Table 5: Mestriylbenzene

[0179]

[0180] The results showed that the addition of mesitylene to an organic phase already containing TBP enhanced the effect in a concentration-dependent manner.

Claims

1. A method for preparing a semipermeable membrane, comprising the following steps: a. Provides an aqueous phase comprising polyfunctional amine monomers and vesicles including aquaporins. b. Cover the surface of the porous support membrane with the aqueous phase. c. Applying an organic phase comprising a nonpolar solvent containing polyfunctional acyl halide monomers, phosphorus-containing compounds, and a co-solvent, and d. Allow the polyfunctional amine monomer and the polyfunctional acyl halide monomer to undergo interfacial polymerization to form a polyamide film composite layer. The ratio of the co-solvent to the phosphorus-containing compound is in the range of 1:2.5 to 4:

1.

2. The method for preparing a semipermeable membrane according to claim 1, wherein, The cosolvent is derived from formula R 1 -OR 2 It means that, among them, R 1 Selected from the group consisting of straight-chain or branched C1-C6 lower alkyl, C1-C6 lower alkenyl, or C1-C6 lower alkynyl groups, optionally substituted by one to three substituents independently selected from the group consisting of: methyl, ethyl, propyl, fluorine, chlorine, bromine, iodine, hydroxyl, aldehyde, carboxylic acid, amine, amide, nitrile, methoxy, ethoxy, propoxy, isopropoxy, and any combination thereof, and R 2 It is selected from the group consisting of: straight-chain or branched C1-C6 lower alkyl, C1-C6 lower alkenyl, C1-C6 lower alkynyl, carbonyl C1-C6 lower alkyl, carbonyl C1-C6 lower alkenyl, carbonyl C1-C6 lower alkynyl, optionally substituted by 1 to 3 substituents selected from the group consisting of: methyl, ethyl, propyl, fluorine, chlorine, bromine, iodine, hydroxyl, aldehyde, carboxylic acid, amine, amide, nitrile, methoxy, ethoxy, propoxy, isopropoxy, and any combination thereof.

3. The method for preparing a semipermeable membrane according to claim 2, wherein, R 1 It is a C1-C6 lower alkyl group and R 2 It is a C1-C6 lower alkyl or carbonyl C1-C6 lower alkyl.

4. The method for preparing a semipermeable membrane according to claim 1, wherein, The cosolvent is selected from the group consisting of ethyl formate, ethyl acetate, and diethyl ether.

5. The method for preparing a semipermeable membrane according to claim 4, wherein, When the cosolvent is ethyl acetate or ethyl formate, the ratio of the cosolvent to the phosphorus-containing compound is in the range of 1:2.5 to 2:2.5, and wherein, when the cosolvent is diethyl ether, the ratio is in the range of 1:2.5 to 2:1.

25.

6. The method for preparing a semipermeable membrane according to claim 1, wherein, The co-solvent is a silane or an aromatic compound.

7. The method for preparing a semipermeable membrane according to claim 6, wherein, The silane is of the general formula X3-Si-R 1 This indicates that X is a halogen independently selected from the group consisting of F, Cl, Br, and I, and R... 1 It is selected from the group consisting of straight-chain or branched C1-C6 lower alkyl, C1-C6 lower alkenyl or C1-C6 lower alkynyl groups, optionally substituted by 1 to 3 substituents independently selected from the group consisting of: methyl, ethyl, propyl, fluorine, chlorine, bromine, iodine, hydroxyl, aldehyde, carboxylic acid, amine, amide, nitrile, methoxy, ethoxy, propoxy, isopropoxy and any combination thereof.

8. The method for preparing a semipermeable membrane according to claim 7, wherein, The R 1 It is a trifluoroC1-C6 alkyl group.

9. The method for preparing a semipermeable membrane according to claim 7, wherein, The R 1 It is trifluoropropyl.

10. The method for preparing a semipermeable membrane according to claim 6, wherein, The aromatic compound comprises a benzene ring, which is optionally substituted by 1 to 6 substituents selected from the group consisting of: methyl, ethyl, propyl, fluorine, chlorine, bromine, iodine, hydroxyl, aldehyde, carboxylic acid, amine, amide, nitrile, methoxy, ethoxy, propoxy, isopropoxy, and any combination thereof.

11. The method for preparing a semipermeable membrane according to claim 10, wherein, The aromatic compound is mesitylene.

12. The method for preparing a semipermeable membrane according to claim 1, wherein, The phosphorus-containing compound is reacted with the polyfunctional acyl halide prior to the step of reacting the polyfunctional acyl halide and the polyfunctional amine.

13. The method for preparing a semipermeable membrane according to claim 1, wherein, The phosphorus-containing compound has an interaction energy with the polyfunctional acyl halide greater than 4.0 kcal / mol.

14. The method for preparing a semipermeable membrane according to claim 1, wherein, The phosphorus-containing compound includes at least one of the following: phosphate ester, phosphite ester, phosphine, phosphine oxide, phosphonate, diphosphite ester, hypophosphite ester, hypophosphite ester, phosphite ester, pyrophosphate ester, pyrophosphoramide, phosphoramide, thiophosphate ester, dithiophosphate ester, and thiophosphoramide ester.

15. The method for preparing a semipermeable membrane according to claim 1, wherein, The phosphorus-containing compound is represented by the following formula: Where Z is either the same or different and is selected from: R 2 OP-(R) 2 )2、P(O)-X2、(P(-R 2 )) m -P-X2、(OP(-R 2 )) m -OPR 2 2. (P(O)(-R) 2 )) m -P(O)-R 2 2 and (OP(O)(-R) 2 )) m -OP(O)-R 2 2; P is phosphorus, O is oxygen, m is an integer from 1 to 5; Y is O or a non-bonded electron pair, R 2 Selected from the group consisting of: straight-chain or branched C1-C6 lower alkyl, C1-C6 lower alkenyl, C1-C6 lower alkynyl, carbonyl C1-C6 lower alkyl, carbonyl C1-C6 lower alkenyl, carbonyl C1-C6 lower alkynyl, optionally substituted by 1 to 3 substituents selected from the group consisting of: methyl, ethyl, propyl, fluorine, chlorine, bromine, iodine, hydroxyl, aldehyde, carboxylic acid, amine, amide, nitrile, methoxy, ethoxy, propoxy, isopropoxy, and any combination thereof, where X is the same or different and selected from: R 3 and R 3 -O,R 3 They are the same or different and are selected from H (hydrogen) and a carbon-containing moiety, wherein the carbon-containing moiety is independently selected from R. 2 Group.

16. The method for preparing a semipermeable membrane according to claim 1, wherein, The phosphorus-containing compound is selected from the group consisting of: trimethyl phosphate, triethyl phosphate, tributyl phosphate, dibutyl phosphite, bis(2-ethylhexyl) phosphite, triphenylphosphine, triphenyl phosphate, triphenylphosphine, tributyl phosphate, di-tert-butyldiisopropylphosphite, dibutyl butylphosphonate, and trioctylphosphine.

17. The method for preparing a semipermeable membrane according to claim 1, wherein, The concentration of the phosphorus-containing compound in the organic phase is 0.2% to 5%.

18. The method for preparing a semipermeable membrane according to claim 1, wherein, The concentration of the co-solvent in the organic phase is 0.005 to 5%.

19. The method for preparing a semipermeable membrane according to claim 1, wherein, The main solvent of the organic phase includes straight-chain or branched C5-C4 compounds. 12 Alkanes.

20. The method for preparing a semipermeable membrane according to claim 19, wherein, The vesicles include poly-block-(2-methyloxazoline)-poly-block-(dimethylsiloxane) (PMOXA-PDMS) and amine-functionalized poly(dimethylsiloxane) as vesicle membrane forming materials.

21. The method for preparing a semipermeable membrane according to claim 1, wherein, The support membrane comprises polysulfone or polyethersulfone polymers.

22. The method for preparing a semipermeable membrane according to claim 1, wherein, The porous support membrane is made of hollow fiber.

23. The method for preparing a semipermeable membrane according to claim 22, wherein, The method includes an additional step of producing a hollow fiber assembly by assembling hollow fiber bundles in a housing, wherein an inlet for delivering a first solution is connected at one end to the inner cavity of the hollow fiber and an outlet is connected at the other end to the inner cavity, and an inlet is provided in the housing for delivering a second solution to an outlet connected to the housing.

24. The method for preparing a semipermeable membrane according to claim 1, wherein, The porous support membrane is a flat plate.

25. The method for preparing a semipermeable membrane according to claim 24, wherein, The method includes an additional step of producing spiral wound components by winding the flat film.

Images