Composite membrane and method for making the same

专利摘要:
The present invention relates to a composite membrane comprising a porous support and a polyamide surface and a method of making the same. The membrane provides improved flow rates and / or rejections. The membrane is operable at low operating pressures. The method includes reacting a polyfunctional amine with a polyfunctional acyl halide to form a polyamide. The method includes contacting the complexing agent with the polyfunctional acyl halide before substantially reacting the polyfunctional acyl halide with the polyfunctional amine. The method is readily applied to commercial scale manufacturing processes and is particularly suitable for the production of nanofiltration and reverse osmosis composite membranes.
公开号:KR20030001430A
申请号:KR1020027013894
申请日:2001-04-09
公开日:2003-01-06
发明作者:미콜스윌리엄이.
申请人:다우 글로벌 테크놀로지스 인크.；
IPC主号:

专利说明:

Composite membrane and method for making the same
[1] Reverse osmosis and nanofiltration membranes are used to separate dissolved or dispersed materials from the feed stream. The separation process typically involves bridging an aqueous solution of feed contacted with one side of the membrane under pressure to prevent permeation of the dissolved or dispersed material, while affecting the permeation of the aqueous phase through the membrane.
[2] Typically, both reverse osmosis and nanofiltration membranes comprise a thin film identification layer immobilized on a porous support, referred to as a "composite membrane". The ultrafiltration and microfiltration membranes may also have a complex arrangement. The support provides physical strength, but due to its porosity the flow is hardly limited. On the other hand, the identification layer is low in porosity and provides a major means of separation of dissolved or dispersed material. Thus, the identification layer generally determines the "rejection rate" (percentage of rejection of a particular dissolved material (ie, solute)) and the "flow rate" (flow rate per unit area of solvent permeating through the membrane) of the membrane.
[3] Reverse osmosis membranes and nanofiltration membranes vary greatly from one another in view of the permeability of different ions and organic compounds. Reverse osmosis membranes are relatively impermeable to virtually all ions, including sodium and chlorine ions. Thus, because reverse osmosis membranes generally have a rejection rate of sodium and chlorine ions relative to the reverse osmosis membrane, from about 95% to about 100%, desalination of brine or seawater for industrial, commercial or domestic use provides relatively salt free water. It is widely used to
[4] Nanofiltration membranes are generally more specific for ion rejection. In general, nanofiltration membranes reject divalent ions including radium, magnesium, calcium, sulfate and carbonate. In addition, nanofiltration membranes are generally impermeable to organic compounds having a molecular weight of at least about 200 Daltons. In addition, nanofiltration membranes have higher flow rates than reverse osmosis membranes at comparable pressures. This property makes nanofiltration membranes useful in a variety of products, such as "softening" water and removing pesticides from water. For example, nanofiltration membranes generally have a sodium chloride removal rate of about 0 to about 95%, but relatively high removal rates for salts such as magnesium sulfate and, in some cases, organic compounds such as atrazine.
[5] Among reverse osmosis and nanofiltration products, it is a particularly useful membrane that the identification layer is polyamide. Polyamide identification layers for reverse osmosis membranes are often obtained by interfacial polycondensation reactions of polyfunctional amine monomers with polyfunctional acyl halide monomers (also referred to as polyfunctional acid halides). See US Pat. No. 4,277,344, herein. Cited by reference]. Polyamide identification layers for nanofiltration membranes are typically obtained by interfacial polymerization of piperazine or amine substituted piperidine or cyclohexane with a multifunctional acyl halide. See US Pat. Nos. 4,769,148 and 4,859,384, Incorporated herein by reference]. Another method of obtaining a polyamide identification layer suitable for nanofiltration is, for example, the methods described in US Pat. Nos. 4,765,897, 4,812,270 and 4,824,574. These patents describe the conversion of reverse osmosis membranes to nanofiltration membranes, such as those described in US Pat. No. 4,277,344.
[6] Composite polyamide membranes are typically prepared by coating a porous support with a polyfunctional amine monomer, mostly from aqueous solutions. Water is the preferred solvent, but non-aqueous solvents such as acetyl nitrile and dimethylformamide (DMF) can also be used. The polyfunctional acyl halide monomer (also referred to as acid halide) is then typically coated on the support from the organic solution. Although no specific order of addition is necessarily required, typically an amine solution is first coated on a porous support and then an acyl halide solution. One or both polyfunctional amines and acyl halides may be coated from solution onto the porous support, but may alternatively be coated in other ways, such as evaporation or in a crude state.
[7] Methods for improving the performance of membranes by adding components to amine and / or acyl halide solutions are described in the literature. For example, US Pat. No. 4,950,404 [Chau] describes a method for increasing the flow rate of a composite membrane by adding a polar aprotic solvent and optional acid acceptor to an aqueous amine solution prior to interfacial polymerization of amines and polycarboxylic acid halides. It is. Similarly, US Pat. Nos. 6,024,873, 5,989,426, 5,843,351, 5,733,602, 5,614,099 and 5,576,057 [Hirose et al.] Disclose 8 to 14 (cal / cm ³ ) ^1/2 prior to interfacial polymerization. The selective addition of alcohols, ethers, ketones, esters, halogenated hydrocarbons, nitrogen containing compounds and sulfur containing compounds with a solubility parameter of to aqueous amine solutions and / or organic acid halide solutions is described.
[8] Methods of improving membrane performance by post-treatment are also known. For example, US Pat. No. 5,876,602 to Jons et al. Discloses treating polyamide composite membranes with an aqueous chlorinating agent to improve flow rates, lower salt permeability, and / or increase membrane stability to bases. Doing. US Pat. No. 5,755,964 [Mickols] describes a process for treating a polyamide identification layer with ammonia or selected amines such as butylamine, cyclohexylamine and 1,6 hexane diamine. US Pat. No. 4,765,897 (Cadotte) describes the treatment of membranes with strong acids followed by rejection enhancers. U.S. Patents 4,765,897, 5,876,602 and 5,755,964 are incorporated herein by reference.
[9] Membranes that have high flow rates at standard operating pressures or that can maintain flow rates at relatively low operating pressures are preferred. Also preferred are membranes having high rejection rates but improved flow rates and / or low pressure requirements. Preference is also given to a process for producing such a membrane, in particular a membrane which can be easily applied to commercial scale membrane fabrication.
[10] Summary of the Invention
[11] The present invention provides an improved composite membrane and a process for preparing the polyamide layer by interfacial polymerization of polyfunctional amines and polyfunctional acyl halides on at least one surface of the porous support. The method is characterized by contacting the complexing agent with the polyfunctional acyl halide prior to and / or during the reaction of the polyfunctional acyl halide with the polyfunctional amine.
[12] It is an object of the present invention to provide an improved membrane having a high flow rate and / or more desirable rejection properties (ie high or low depending on the end use of the membrane). It is a further object of the present invention to provide a membrane which is operable at a relatively low pressure while still providing a flow rate and / or rejection rate. It is yet another object of the present invention to provide a method for preparing the membrane, including a method that can be easily applied to commercial scale membrane fabrication. The method is particularly suitable for making nanofiltration and reverse osmosis membranes.
[13] The composite membranes of the present invention are also referred to as polyfunctional amine monomers ("amines", "polyamines" and "polyfunctional amines"-each term is intended to use a single species or a combination of multiple species of amines) And polyfunctional acyl halides (also referred to as "acyl halides", "acid halides" and "polyfunctional acid halides"-each term is intended to use a single species or a combination of multiple species of acyl halides). Prepared by interfacial polymerization at one or more surfaces of the support. Typically, amines and acyl halides are transferred to the porous support by the coating step method from solution, amines are typically coated from aqueous solutions, and acyl halides are coated from non-aqueous, organic based solutions. The coating step is "out of order", i.e., not in a particular order, but it is preferred that the amine is first coated on the support and then the acyl halide. Coating is achieved by the use of spraying, rolling, dipping tanks and the like. Excess solution may be removed from the support by air and / or water cutting, dryers, ovens, or the like.
[14] The polyfunctional amine monomer used in the present invention may have a primary or secondary amino group and may be aromatic (eg 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 such as ethylenediamine, propylenediamine and tris (2 -Diaminoethyl) amine). Examples of preferred amine species include primary aromatic amines having 2 or 3 amino groups, in particular m-phenylene diamine, and secondary aliphatic amines having 2 amino groups, especially piperazine. Typically, amines are coated with a microporous support in water as a solvent. The most common aqueous solutions contain about 0.1 to about 20 weight percent, more preferably about 0.5 to about 6 weight percent amine. After being coated on the microporous support, excess aqueous amine solution can optionally be removed. The amine solution need not be aqueous and is preferably immersed using the non-polar non-aqueous solvent described below.
[15] As described above, polyfunctional acyl halides can be transported from the vapor phase (in the case of polyfunctional acyl halides with sufficient vapor pressure), but monomeric polyfunctional acyl halides are preferably coated from a nonpolar solvent. The polyfunctional acyl halides are preferably aromatic and contain at least two, preferably three, acyl halide groups per molecule. Due to their low cost and high utility, chlorides are generally preferred over the corresponding bromide or iodine. Preferred polyfunctional acyl halides are trimesoyl chloride (TMC). The polyfunctional acyl halides are typically dissolved in the range of 0.01 to 10.0 weight percent (more preferably 0.05 to 3 weight percent) in nonpolar organic solvents and are transferred as part of the continuous coating operation. Suitable nonpolar solvents are solvents which can dissolve polyfunctional acyl halides and precipitate with water. Preferred solvents include those which do not threaten the ozone layer and are sufficiently stable in terms of flash point and flammability and can be processed without taking extreme precautions. Although high boiling point hydrocarbons, ie hydrocarbons having a boiling point above about 90 ° C. such as C _8-14 hydrocarbons and mixtures thereof, have a more suitable flash point than C _5-7 hydrocarbons, but they are less volatile.
[16] When in contact with each other, the polyfunctional acyl halides and polyfunctional amines react at their surface boundaries to form a polyamide identification layer. Typically, after optionally removing excess liquid by methods such as, for example, air cutting, water bath (s), dryers, etc., the reaction time is less than 1 second, but the contact time is often 1 to 60 seconds. Removal of excess water and / or organic solvent can be used for air drying at room temperature, but is mostly accomplished by drying at elevated temperatures, for example from about 40 ° C to about 120 ° C.
[17] Unless theoretically limited, it is believed that the acyl halide functional group of the polyfunctional acyl halide monomer is often hydrolyzed before contact with the amine functional group. Under typical manufacturing conditions, such hydrolysis of acyl halide functional groups is substantially irreversible. That is, under the time, temperature and concentration typically used in commercial scale membrane preparation, it is not believed that amine functional groups react substantially with hydrolyzed acyl halide groups. Hydrolysis of these acyl halide groups is believed to degrade membrane performance.
[18] Unless theoretically limited, complexing agents are believed to be able to form "bonds" with polyfunctional acyl halide monomers when used in accordance with the methods of the present invention. It is believed that the formation of such bonds significantly reduces the hydrolysis of acyl halide functional groups, and sufficiently allows subsequent reactions between acyl halide and amine functional groups, leading to the aforementioned improvements in membrane performance. Lose.
[19] The term "bond" is intended to describe the chemical interaction formed between the complexing agent and the polyfunctional acyl halide before or during the reaction of the amine with the acyl halide functional group. This bond may also be described as meaning removal of the repulsive force between the polyfunctional acyl halide and other solution components.
[20] Another method for describing the interaction between acyl halides and complexing agents is the "total energy change" produced from combinations thereof. In nontechnical terms, this is the energy change resulting from the bond formation between the complexing agent and the acyl halide. In general, the total energy "U" can be defined by Equation 1 below (see H. Callan's "Thermodynamics", John Wily & Son, New York, 1960):
[21]
[22] "ΔU", that is, the change in total energy produced (Δ) from separate chemical species, is defined by Equation 2 below:
[23]
[24] In Equation 2 above,
[25] u is the chemical potential of each chemical species (eg TMC and complexing agent),
[26] N is the number of moles of each chemical species,
[27] T is temperature
[28] S is entropy,
[29] P is the pressure,
[30] V is the volume of the system,
[31] i and m are integers starting with "1" and m is the total number of chemical species in the system.
[32] Total energy is closely related to some other indication of energy with experimental limitations. For example, free energy "μ" is commonly used for reactions that occur at atmospheric pressure and is represented by Equation 3 below:
[33]
[34] In Equation 3 above,
[35] n is equal to the number of moles of the species bound (e.g., the reaction product of the acyl halide monomer and the complexing agent),
[36] G is the Gibbs free energy,
[37] T is temperature
[38] S is entropy,
[39] P is the pressure,
[40] V is the volume of the system.
[41] G is defined according to equation 4:
[42]
[43] In Equation 4 above,
[44] H is the enthalpy of the system.
[45] All citations to terms and symbols related to energy are intended to be consistent with standard chemical agreements.
[46] When combined with an acyl halide, the complexing agent of the present invention results in a total energy change (ΔU) of about 3.5-20 kcals / mole, more preferably about 5-15 kcals / mole, more preferably 5-10 kcals / mole. It is desirable to. In the present invention, the total energy change resulting from the combination of acyl halide and complexing agent is approximately equal to the change in Gibbs free energy and enthalpy, ie U ≒ G ≒ H. Thus, one of ordinary skill in the art can determine the suitability of a complexing agent for using a particular acyl halide, typically by measuring the enthalpy (H) resulting from these formulations. Calorimetry to measure the enthalpy of a system is well known.
[47] In many embodiments, the total energy and / or enthalpy of the interaction of the complexing agent and acyl halide obtained is approximately equal to the total energy and / or enthalpy of the system used under the manufacturing conditions. In other words, the change in the total energy or enthalpy of the interaction between the acyl halide and the complexing agent is determined by the enthalpy of the system relative to the complexing agent added to the acyl halide coating solution including, for example, acyl halides, solvents, additives, impurities, etc. It can be inferred by measuring the change. In this embodiment, the complexing agent is contacted with the acyl halide from the amine solution, and the applicable "system" can be further complicated by additional chemical species such as, for example, amines, water, and the like. In the final analysis, the total energy change results from the interaction between the acyl halide and the most suitable complexing agent. In other words, it should be evaluated that the reaction medium may have a sufficient effect on the change in the total free energy of the system. For example, in a preferred embodiment, both the acyl halide and the complexing agent are substantially soluble in the solution to be coated.
[48] Too weak binding (ie, a total energy value of less than about 3.5 kcals / mole) results in binding that does not sufficiently interfere with hydrolysis of the acyl halide functional group. As described below, one measure of sufficiently strong binding is the presence of a "detectable amount" of complexes "preserved" in the polyamide, even after the post-cleaning of the membrane. On the other hand, too strong bonds (ie, a total energy of at least about 20, preferably 15 kcals / mole) do not sufficiently allow substitution and reaction by amines during membrane formation, thus preventing the formation of the desired polyamide. An example of too strong bonding is the hydrolysis of the acid chloride groups of TMC under conventional manufacturing conditions resulting in a total energy value of at least about 25 kcals / mole.
[49] In order to obtain all the advantages of the present invention, it is believed that the bond between the complexing agent and acyl halide is formed before or during the reaction between the acyl halide and the amine. Therefore, it is believed that the timing and method of addition of the complexing agent is important. For example, the benefits of the present invention are not achieved by the addition of phosphoric acid alone after substantially acyl halides and amines react (see US Pat. No. 4,765,897). In addition, the advantages of the present invention are not achieved even when contacted in a manner that does not allow the bond formation of the complexing agent and acyl halide. For example, when a particular complexing agent is insufficiently dissolved or dispersed in an acyl halide solution, all of the advantages of the present invention are not realized because of an inadequate level of binding. As a result, a preferred aspect of the present invention is the use of a complexing agent which is substantially dissolved in the acyl halide solution to facilitate formation of the bond with the acyl halide. As with other cases, preferred complexes have a solubility parameter of about 15 to about 26, more preferably 18 to 23J ^1/2 cm ^-3/2 .
[50] In a preferred embodiment, the complexing agent is added directly to the acyl halide solution before the acyl halide and amine solution are contacted (eg, coated), thereby allowing sufficient opportunity to form a bond before the reaction between the amine and acyl halide. Alternatively, the acyl halides and complexing agents can be contacted in the "unprocessed state" and then added to the solution for coating.
[51] In an alternative embodiment, the acyl halide solution may be contacted with a polyfunctional amine solution while simultaneously contacting the complexing agent (s) with an acyl halide solution (eg, via spraying). In this embodiment, the complexing agent is essentially contacted with the acyl halide solution at the same time as the acyl halide and amine solution contacting before the reaction between the amine and acyl halide is terminated. In this embodiment, the acyl halide and the complexing agent form a complex for a very short time before the reaction between the acyl halide and the amine is terminated. Alternatively, the complexing agent may be contacted with the acyl halide and amine solution and then with the acyl halide solution before the reaction is complete. As indicated above, this embodiment provides a very short time to form the complex before the reaction between the acyl halide and the amine is terminated.
[52] In another embodiment, the complexing agent may be coated on the support or added to the amine solution prior to contacting the amine with the acyl halide solution. This approach is undesirable because it is difficult to transfer the complexing agent to the acyl halide in such a way as to form a suitable complex before the reaction between the acyl halide and the amine is terminated. However, one complementary approach involves forming a high internal phase emulsion of the complexing agent in the amine solution, thereby providing a relatively uniform transfer of the complexing agent to the acyl halide during the reaction between the acyl halide and the amine. The formation of high internal phase emulsions is well known and described in US Pat. No. 5,977,194, which is incorporated herein by reference. Another suitable approach is to select a complexing agent that is sufficiently soluble in an acyl halide solution (e.g., organic solution) while having sufficient solubility in an amine solution (e.g., an aqueous solution) to disperse uniformly, thereby providing a sufficient amount of complexing. That I served as an acyl halide before the reaction between the acyl halide and the amine was terminated.
[53] The above described embodiments can be used in combination, for example, a complexing agent can be added to both the acyl halide and amine solution prior to contact with the solution. Alternatively, the complexing agent may be added to the solution via spraying or vapor deposition during the step of coating the solution.
[54] According to the method the means for detecting whether the complexing agent (s) has been in successful contact with the acyl halide is the presence of a "detectable amount" of the "conserved" complexing agent in the polyamide membrane. The term "conserved" means that the membrane is supplied at a flow rate of 24 gfd (gallons per square foot per day) (0.0011 cm / sec) through the membrane for 24 hours at 25 ° C. using a permeation recovery between 0.5% and 25%. It is intended to mean that the complexing agent remains in the polyamide membrane (eg, bonds, covalent bonds, complexes, weak bonds, etc.) even after being operated in reverse osmosis using pure water. This is accomplished by using test cells commonly used in test membranes. For example, the test cell may be of "flat and frame" design and may include helical elements made using membranes.
[55] For example, the purified water is washed across the polyamide membrane at a pressure of about 70 pounds per square inch for 24 hours at 25 ° C. This washing removes excess material that is present initially but does not benefit the present invention. For example, it is well known that phosphoric acid can be added to the amine solution as a pH buffer. In this embodiment, a portion of the phosphoric acid may be present in the membrane initially produced, but the phosphoric acid is not contacted with the acyl halides in a manner that allows sufficient bonding, and the phosphoric acid is not preserved and removed from the membrane during use or washing. The use of phosphoric acid in the prior art can be used in conjunction with the present invention, but in embodiments of the prior art it is not possible to produce "conserved" phosphoric acid and result in improved membrane performance due to the present invention.
[56] The term “detectable amount” is intended to mean a sufficient amount of conserved complex that exists to be able to be measured, identified or otherwise detected by quantitative or qualitative analysis. Detection of such complexing agents in the membrane is carried out by all suitable analytical techniques, but typically relatively low amounts of complexing agents are used, for example gas chromatography, X-ray fluorescence (XRF), secondary ion mass spectroscopy. Relatively high sensitivity analytical techniques are preferred, such as colorimetric analysis of IR and totally burned polyamides. Typically, the detection of the complexing agent is concentrated at the binding center of the complexing agent. As described in more detail below, bond centers often include metals such as, for example, Pb, Fe, Cr, Ni, Co, Cu, Zn, Al, As, Sb, Te, and the like, but P, Si, It may also contain other elements such as Se, Ge and the like. One specific X-ray fluorescence detection methodology is particularly suitable for detecting phosphorus containing complexing agents, for example by boiling the membrane in water for about 30 minutes and then using a suitable solvent such as methylene chloride to form the porous support. Dissolution and extraction of a portion of the polyamide polymer (eg 100 mg) from the porous support, such as extensive extraction of the polyamide in the same solvent. The polyamide can then be separated and compressed into a 13 mm diameter disk using die and hydraulic pressure (10,000 lbs load). The resulting disk is placed between two layers of polypropylene sample support film (thickness 6.0 μ) and attached to a 30 mm diameter Chemplex XRF sample cup using a standard support ring. Samples can be measured in plastic with Pb mask inserted. Measurements can be obtained on average on both sides of the disc. After preparation, samples can be analyzed using a Philips PW1480 wavelength dispersed X-ray fluorescence spectrometer equipped with a scandium anode 3KW X-ray tube. For example, phosphorus can be measured by using K α X-ray intensity with a device operated under the following conditions: 50 kV, 50 mA, germanium crystal (2d = 6.532 kW), gas flow proportional detector (argon / methane), top And bottom identification level 80/25, He purification. K α peak can be measured at 2θ angle of 141.035 and background can be measured at + and − offset of 1.5. Peak and background measurements are typically performed for 10 seconds each.
[57] In a preferred embodiment, the polyamide composite membrane has at least about 25 μg (preferably at least 50 μg, more preferably at least 100 μg, in certain embodiments at least 200 μg) of the binding center of the “conserved” complexing agent to every gram of polyamide Include). The elements that make up the binding center of the complexing agent are typically not present during conventional membrane fabrication. Accordingly, these elements serve as good indicators of whether the complexing agent works effectively during membrane preparation.
[58] As indicated, the conserved complexing agent is believed to be the result of the formation of complexes, conserved monomers and / or reaction products between the complexing agent and the polyamide. Though depending on the relative density of the polyamide layer, most membranes of the present invention includes the complex of the membrane more per 1m ² 0.02㎍, more generally comprises a complex of at least about 1㎍ membrane per 1m ^2.
[59] The complexing agent of the present invention is not particularly limited, and compounds of different species may be combined and used. However, preferred species are not spontaneously flammable and are sufficiently stable in air and water (ie, the species do not cause degradation, sensitivity or severe reactions with water or air during the time applied to the process), for example in severe environments It has suitable industrial hygiene properties, with no risk of danger, no need for expensive operation, and no serious stability problems. The complexing agent is "substantially soluble" in an organic solution as described herein. The term "substantially soluble" is intended to mean that a sufficient amount of complexing agent is dissolved in solution to produce a final membrane with improved flow rate, rejection and / or low operating pressure compared to the same membrane prepared without complexing agent. do. Further evidence that the complexing agent is "substantially soluble" is the presence of a detectable amount of complexing agent preserved in the polyamide layer. When used at effective concentrations, the complexing agent dissolves and forms a single, uniform phase in the organic solution described above. Preferred complexing agents have a solubility parameter of about 15 to about 26, more preferably 18 to 23J ^1/2 cm ^-3/2 .
[60] Without considering the means of contact of the complexing agent with the acyl halide solution, the amount of the complexing agent is preferably stoichiometrically related to the amount of the polyfunctional acyl halide. Preferred stoichiometric ratios of the complexing agent and the polyfunctional acyl halide are about 1: 5 to about 5: 1, with 1: 1 to about 3: 1 being most preferred. Even if desired, no stoichiometric ratio of the complexing agent is required. When formulated directly with an acyl halide solution, the complexing agent is typically included at from about 0.001 to about 2 weight percent based on the acyl halide solution. When used according to alternative embodiments as described above, large amounts of complexing agents may be necessary.
[61] Unlike conventional interfacial polymerization of polyfunctional acyl halides and polyfunctional amines in which the relative concentrations of acyl halide species are controlled, in the present invention, the relative concentrations of amine species can play a more sufficient role. Through routine experimentation, one of ordinary skill in the art will understand the specific properties and concentrations of complexing agent (s), acyl halides and amines, the optimum concentrations of polyfunctional amines to obtain the desired membrane performance.
[62] Complexing agents include a wide variety of compounds of formula 1:
[63] α (L _x β) _y
[64] In Formula 1 above,
[65] α represents (a) Group IIIA to VIB elements (ie, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB and VIB groups) of the conventional IUPAC periodic table and (b) 3 to 6 It is a bond center containing no sulfur selected from periodic elements (ie, regions starting from Na, K, Rb and Cs).
[66] Group IIIA-VIB elements of a typical IUPAC periodic table correspond to groups 3-16 of the "new notation" of the IUPAC periodic table and IIIB-VIA groups of the CAS version of the periodic table. In order to avoid all confusion, the tabular IUPAC periodic table is incorporated herein by reference, that is, group IIIA elements correspond to columns starting from Sc, Y, La, etc., and group VIB elements are O, S, Se, Te, Corresponds to the column starting with PO. Specific examples are as follows: (1) Metals: aluminum, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, yttrium, zirconium, niobium, molybdenum, technetium, Ruthenium, rhodium, palladium, silver, cadmium, indium, chemotaxis, antimony, tellurium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, ruthenium, hafnium , Tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, bismuth (bismuth is typically not preferred) and polonium; (2) semiconductors: silicon, selenium and germanium, and (3) phosphorus. Particularly preferred bonding centers include: Al, Si, P, As, Sb, Se and Te, and metals such as Fe, Cr, Co, Ni, Cu and Zn. L is any chemical bond group and is the same or different and is selected from the following bonds: carbon containing moieties such as aromatic groups, alkanes, alkenes, -O-, -S-, -N-,- H-, -P-, -OP- and -OPO-, wherein each group may or may not be substituted. β is a soluble group, is the same or different, contains 1 to 12 carbon atoms, may be substituted or unsubstituted, and may comprise an internal bonding group as defined in L. Examples include aliphatic and arene groups, aromatic groups, heterocyclic groups and alkyl groups having 1 to 6 carbon atoms. "x" is an integer of 0-1, "y" is an integer of 1-5, preferably 2-4.
[67] Depending on the particular solvent (s) and acyl halide species used, the following complexing agents are generally useful in the present invention: tri-phenyl derivatives of phosphorus (such as phosphine, phosphate), bismuth, arsenic and antimony; Alkanes oxy esters of phosphorus including tributyl and dibutyl phosphite; Organometallic complexes such as ferrocene and tetraethyl lead and acetylacetonate complexes of iron (II), iron (III), cobalt (III) and Cr (III).
[68] Complexing agents comprising phosphorus binding centers have been found to be particularly preferred. A preferred class of such phosphorus containing compounds are those of the formula
[69]
[70] In Formula 2 above,
[71] Z is the same or different and X, OP- (X) ₂ , P (O) -X ₂ , (P (-X)) _m -PX ₂ , (OP (-X)) _m -OPX ₂ , (P (O) (-X)) _m -P (O) -X ₂ and (OP (O) (-X)) _m -OP (O) -X ₂ [where P is phosphorus and O is oxygen, m is an integer from 1 to 5, Y is O (oxygen) or an unbonded electron pair of formulas 3 and 4, respectively, X is the same or different and comprises R or one or more oxygen and / or alkyl bond (s) Is selected from R (e.g., ROR, OR, etc.), wherein R is the same or different and is selected from H (hydrogen) and / or carbon containing moieties), and the Z group is substantially in the organic solution. It is preferred to be selected in order to bring about a phosphorus containing compound which can be dissolved.
[72]
[73]
[74] "Identical or different" is intended to mean that individual groups represented by a single symbol, eg "R", may vary within a given compound. For example, for every given compound one R group may be hydrogen, while the other R group may be a butyl group.
[75] The term "carbon containing moiety" refers to a straight or branched acyclic group (e.g., unsubstituted or amide group, ether group, ester group, sulfone group, carbonyl group, anhydride, cyanide, nitrile, isocyanate, urethane, β-hydroxy Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, 2-pentyl, 3-pentyl, tert-butyl, etc. which may be substituted by esters, double bonds, triple bonds, etc.) and cyclic groups [e.g. Cyclopentyl, cyclohexyl, aromatic (e.g. phenyl, heterocyclic (e.g. pyridine), etc.), which may be unsubstituted or substituted with methyl, ethyl, propyl, hydroxyl, amide, ether, sulfone, carbonyl, ester, etc. Is intended to mean]. The cyclic moiety may be bonded to the phosphorus atom using, for example, an alicyclic bonding group such as methyl, ethyl or the like.
[76] Preferred carbon containing moieties are unsubstituted straight or branched C _1-12 groups, more preferably methyl, ethyl, propyl, isopropyl, butyl, 2-methyl butyl, 3-methyl butyl, 2-ethyl butyl, pentyl, hexyl C _1-8 alicyclic groups such as the like. In addition, preferred moieties include phenyl groups.
[77] Preferred examples of this class of compounds are compounds of formulas 5-10.
[78]
[79]
[80]
[81]
[82]
[83]
[84] In Formula 5 to Formula 10 above,
[85] R, P and O are as defined above.
[86] Such phosphorus containing compounds are commercially available or can be synthesized using known methodologies. See US Pat. No. 2,648,696 to Wetstone, which is incorporated herein by reference; And Aharoni et al., Journal of Polymer Science, Volume 22, 2579-2599.
[87] The term phosphorus used herein is consistent with that used in D. Corbridge's Studies in Inorganic Chemistry, 6: Phosphorous-An Outline of its Chemistry, Biochemistry and Technology, third ed., (Eelsevier 1985). It is intended. Examples of applicable phosphorus containing compounds include phosphates (eg phosphate esters), phosphites, phosphines, phosphine oxides, phosphonates (including diphosphonates), phosphinates, phosphinites, phosphonites, pyrophosphates , Pyrophosphoamide, phosphoramide, phosphorothionate (including phosphodithionate), phosphor amido thionate and phosphorothioate (including phosphonodithioate). A restrictive list of specific examples of each class is provided below.
[88] Specific examples of tri-phosphates are as follows:
[89] Tri-methyl phosphate, tri-ethyl 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, tri- (1-CH ₃ (CH ₂ ) ₈ ) phosphate, tri- (2-CH ₃ (CH ₂ ) ₈ ) phosphate, tri- (3-CH ₃ (CH ₂ ) ₈ ) phosphate, tri- (4-CH ₃ (CH ₂ ) ₈ ) phosphate, tri- (1-CH ₃ (CH ₂ ) ₉ ) phosphate , Tri- (2-CH ₃ (CH ₂ ) ₉ ) phosphate, tri- (3-CH ₃ (CH ₂ ) ₉ ) phosphate, tri- (4-CH ₃ (CH ₂ ) ₉ ) phosphate, tri- (5 -CH ₃ (CH ₂ ) ₉ ) phosphate, tri- (1-CH ₃ (CH ₂ ) ₁₀ ) phosphate, tri- (2-CH ₃ (CH ₂ ) ₁₀ ) phosphate, tri- (3-CH ₃ (CH ₂ ) ₁₀ ) phosphate, tri- (4-CH ₃ (CH ₂ ) ₁₀ ) phosphate, tri- (5-CH ₃ (CH ₂ ) ₁₀ ) phosphate, tri- (1-CH ₃ (CH ₂ ) ₁₁ ) phosphate , Tri- (2-CH ₃ (CH ₂ ) ₁₁ ) phosphate, tri- (3-CH ₃ (CH ₂ ) ₁₁ ) phosphate, tri- (4-CH ₃ (CH ₂ ) ₁₁ ) phosphate, tri- (5 -CH ₃ (CH ₂ ) ₁₁ ) phosphate, tri- (6-CH ₃ (CH ₂ ) ₁₁ ) phosphate, tri- (1-CH ₃ (CH ₂ ) ₁₂ ) phosphate, tri- (2-CH ₃ (CH ₂ ) ₁₂ ) phosphate, tri- (3-CH ₃ (CH ₂ ) ₁₂ ) phosphate, tri- (4-CH ₃ (CH ₂ ) ₁₂ ) phosphate, tri- (5-CH ₃ (CH ₂ ) ₁₂ ) phosphate , tri- (6-CH ₃ (CH _{2) 12)} phosphate, tri- (methyl pentyl) phosphate, tri- (ethyl Tyl) phosphate, tri- (methyl hexyl) phosphate, tri- (ethyl hexyl) phosphate, tri- (propyl hexyl) phosphate, tri- (methyl heptyl) phosphate,, tri- (ethyl heptyl) phosphate, tri- (diethyl Heptyl) phosphate, tri- (methyl octyl) phosphate, tri- (dimethyl octyl) 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- (tert-three) phosphate, methyl di- (1-pentyl) Phosphate, methyl di- (2-pentyl) phosphate, methyl di- (3-pentyl) phosphate, methyl di- (1-hexyl) phosphate, methyl 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- Yl) phosphate, methyl di- (1-octyl) phosphate, methyl di- (2-octyl) phosphate, methyl di- (3-octyl) phosphate, methyl di- (4-octyl) phosphate, methyl di- (1- CH ₃ (CH ₂ ) ₈ ) phosphate, methyl di- (2-CH ₃ (CH ₂ ) ₈ ) phosphate, methyl di- (3-CH ₃ (CH ₂ ) ₈ ) phosphate, methyl di- (4-CH ₃ (CH ₂ ) ₈ ) phosphate, methyl di- (1-CH ₃ (CH ₂ ) ₉ ) phosphate, methyl di- (2-CH ₃ (CH ₂ ) ₉ ) phosphate, methyl di- (3-CH ₃ (CH ₂ ) ₉ ) phosphate, methyl di- (4-CH ₃ (CH ₂ ) ₉ ) phosphate, methyl di- (5-CH ₃ (CH ₂ ) ₉ ) phosphate, methyl di- (1-CH ₃ (CH ₂ ) ₁₀ ) phosphate, methyl di- (2-CH ₃ (CH ₂ ) ₁₀ ) phosphate, methyl di- (3-CH ₃ (CH ₂ ) ₁₀ ) phosphate, methyl di- (4-CH ₃ (CH ₂ ) ₁₀ ) Phosphate, methyl di- (5-CH ₃ (CH ₂ ) ₁₀ ) phosphate, methyl di- (1-CH ₃ (CH ₂ ) ₁₁ ) phosphate, methyl di- (2-CH ₃ (CH ₂ ) ₁₁ ) phosphate, methyl di _{- (3-CH 3 (CH} 2) 11) phosphine, pay , Methyl di _{- (4-CH 3 (CH} 2) 11) phosphate, methyl di _{- (5-CH 3 (CH} 2) 11) phosphate, methyl di _{- (6-CH 3 (CH} 2) 11) phosphate, methyl Di- (1-CH ₃ (CH ₂ ) ₁₂ ) phosphate, methyl di- (2-CH ₃ (CH ₂ ) ₁₂ ) phosphate, methyl di- (3-CH ₃ (CH ₂ ) ₁₂ ) phosphate, methyl di- (4-CH ₃ (CH ₂ ) ₁₂ ) phosphate, methyl di- (5-CH ₃ (CH ₂ ) ₁₂ ) phosphate, methyl di- (6-CH ₃ (CH ₂ ) ₁₂ ) phosphate, ethyl di- (1 -Propyl) phosphate, ethyl di- (2-propyl) phosphate, ethyl di- (1-butyl) phosphate, ethyl di- (2-butyl) phosphate, ethyl di- (l-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-oxyl) phosphate, ethyl di- (2-octyl) phosphate, ethyl di- (3-octyl) Phosphate, ethyl di- (4-octyl) phosphate, ethyl di- (1-CH ₃ (CH ₂ ) ₈ ) phosphate, ethyl di- (2-CH ₃ (CH ₂ ) ₈ ) phosphate, ethyl di- (3- CH ₃ (CH ₂ ) ₈ ) phosphate, ethyl di- (4-CH ₃ (CH ₂ ) ₈ ) phosphate, ethyl di- (1-CH ₃ (CH ₂ ) ₉ ) phosphate, ethyl di- (2-CH ₃ (CH ₂ ) ₉ ) phosphate, ethyl di- (3-CH ₃ (CH ₂ ) ₉ ) phosphate, ethyl di- (4-CH ₃ (CH ₂ ) ₉ ) phosphate, ethyl di- (5-CH ₃ (CH ₂ ) ₉ ) phosphate, ethyl di- (1-CH ₃ (CH ₂ ) ₁₀ ) phosphate, ethyl di- (2-CH ₃ (CH ₂ ) ₁₀ ) phosphate, ethyl di- (3-CH ₃ (CH ₂ ) ₁₀ ) phosphate, ethyl di- (4-CH ₃ (CH ₂ ) ₁₀ ) phosphate, ethyl di- (5-CH ₃ (CH ₂ ) ₁₀ ) phosphate, ethyl di- (1-CH ₃ (CH ₂ ) ₁₁ ) phosphate, ethyl di _{- (2-CH 3 (CH} 2) 11) Scan sulfate, ethyl di _{- (3-CH 3 (CH} 2) 11) phosphate, ethyl di _{- (4-CH 3 (CH} 2) 11) phosphate, ethyl di _{- (5-CH 3 (CH} 2) 11) phosphate , Ethyl di- (6-CH ₃ (CH ₂ ) ₁₁ ) phosphate, ethyl di- (1-CH ₃ (CH ₂ ) ₁₂ ) phosphate, ethyl di- (2-CH ₃ (CH ₂ ) ₁₂ ) phosphate, ethyl Di- (3-CH ₃ (CH ₂ ) ₁₂ ) phosphate, ethyl di- (4-CH ₃ (CH ₂ ) ₁₂ ) phosphate, ethyl di- (5-CH ₃ (CH ₂ ) ₁₂ ) phosphate, ethyl di- (6-CH ₃ (CH ₂ ) 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-CH ₃ (CH ₂ ) ₈ ) phosphate, 1-propyl di- (2-CH ₃ (CH ₂ ) ₈ ) phosphate, 1-propyl di- (3-CH ₃ (CH ₂ ) ₈ ) phosphate , 1-propyl di- (4-CH ₃ (CH ₂ ) ₈ ) phosphate, 1-propyl di- (1-CH ₃ (CH ₂ ) ₉ ) phosphate, 1-propyl di- (2-CH ₃ (CH ₂₎ ) ₉ ) phosphate, 1-propyl di- (3-CH ₃ (CH ₂ ) ₉ ) phosphate, 1-propyl di- (4-CH ₃ (CH ₂ ) ₉ ) phosphate, 1-propyl di- (5-CH ₃ (CH ₂ ) ₉ ) phosphate, 1-propyl di- (1-CH ₃ (CH ₂ ) ₁₀ ) phosphate, 1-propyl di- (2-CH ₃ (CH ₂ ) ₁₀ ) phosphate, 1-propyl di- _{(3-CH 3 (CH 2} ) 10) phosphate, 1-au Peel-di _{- (4-CH 3 (CH} 2) 10) phosphate, 1-propyl di _{- (5-CH 3 (CH} 2) 10) phosphate, 1-propyl di _{- (1-CH 3 (CH} 2) 11) Phosphate, 1-propyl di- (2-CH ₃ (CH ₂ ) ₁₁ ) phosphate, 1-propyl di- (3-CH ₃ (CH ₂ ) ₁₁ ) phosphate, 1-propyl di- (4-CH ₃ (CH ₂ ) ₁₁ ) phosphate, 1-propyl di- (5-CH ₃ (CH ₂ ) ₁₁ ) phosphate, 1-propyl di- (6-CH ₃ (CH ₂ ) ₁₁ ) phosphate, 1-propyl di- (1- CH ₃ (CH ₂ ) ₁₂ ) phosphate, 1-propyl di- (2-CH ₃ (CH ₂ ) ₁₂ ) phosphate, 1-propyl di- (3-CH ₃ (CH ₂ ) ₁₂ ) phosphate, 1-propyl di -(4-CH ₃ (CH ₂ ) ₁₂ ) phosphate, 1-propyl di- (5-CH ₃ (CH ₂ ) ₁₂ ) phosphate, 1-propyl di- (6-CH ₃ (CH ₂ ) ₁₂ ) phosphate, 2-propyl di- (1-butyl) phosphate, 2-propyl di- (2-butyl) phosphate, 2-propyl di- (l-tert-butyl) phosphate, 2-propyl di- (2-tert- Butyl) phosphate, 2-propyl di- (1-pentyl) phosphate, 2-propyl di- (2- Tyl) 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 di- (2-octyl) phosphate, 2-propyl di- (3-octyl) phosphate, 2-propyl di- (4-octyl) phosphate, 2- Propyl di- (1-CH ₃ (CH ₂ ) ₈ ) phosphate, 2-propyl di- (2-CH ₃ (CH ₂ ) ₈ ) phosphate, 2-propyl di- (3-CH ₃ (CH ₂ ) ₈ ) Phosphate, 2-propyl di- (4-CH ₃ (CH ₂ ) ₈ ) phosphate, 2-propyl di- (1-CH ₃ (CH ₂ ) ₉ ) phosphate, 2-propyl di- (2-CH ₃ (CH ₂ ) ₉ ) phosphate, 2-propyl di- (3-CH ₃ (CH ₂ ) ₉ ) phosphate, 2-propyl di- (4-CH ₃ (CH ₂ ) ₉ ) phosphate, 2-propyl di- (5- CH ₃ ( CH ₂ ) ₉ ) phosphate, 2-propyl di- (1-CH ₃ (CH ₂ ) ₁₀ ) phosphate, 2-propyl di- (2-CH ₃ (CH ₂ ) ₁₀ ) phosphate, 2-propyl di- (3 -CH ₃ (CH ₂ ) ₁₀ ) phosphate, 2-propyl di- (4-CH ₃ (CH ₂ ) ₁₀ ) phosphate, 2-propyl di- (5-CH ₃ (CH ₂ ) ₁₀ ) phosphate, 2-propyl Di- (1-CH ₃ (CH ₂ ) ₁₁ ) phosphate, 2-propyl di- (2-CH ₃ (CH ₂ ) ₁₁ ) phosphate, 2-propyl di- (3-CH ₃ (CH ₂ ) ₁₁ ) phosphate , 2-propyldi- (4-CH ₃ (CH ₂ ) ₁₁ ) phosphate, 2-propyl di- (5-CH ₃ (CH ₂ ) ₁₁ ) phosphate, 2-propyl di- (6-CH ₃ (CH ₂₎ ) ₁₁ ) phosphate, 2-propyl di- (1-CH ₃ (CH ₂ ) ₁₂ ) phosphate, 2-propyl di- (2-CH ₃ (CH ₂ ) ₁₂ ) phosphate, 2-propyl di- (3-CH ₃ (CH ₂ ) ₁₂ ) phosphate, 2-propyl di- (4-CH ₃ (CH ₂ ) ₁₂ ) phosphate, 2-propyl di- (5-CH ₃ (CH ₂ ) ₁₂ ) phosphate, 2-propyl di- (6-CH ₃ (CH ₂ ) ₁₂ ) phosphate, butyl di- (l-tert-butyl) phosphate, butyl di- (2-tert-butyl) phosphate, butyl di- (1-pentyl) phosphate, butyl di- (2-pentyl) phosphate, butyl di- (3-pentyl) phosphate, butyl di- (1-hexyl) phosphate, 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-CH ₃ (CH ₂ ) ₈ ) phosphate, butyl di- (2-CH ₃ (CH ₂ ) ₈ ) phosphate, butyl di- (3-CH ₃ (CH ₂ ) ₈ ) phosphate, butyl di -(4-CH ₃ (CH ₂ ) ₈ ) phosphate, butyl di- (1-CH ₃ (CH ₂ ) ₉ ) phosphate, butyl di- (2-CH ₃ (CH ₂ ) ₉ ) phosphate, butyl di- ( 3-CH ₃ (CH ₂ ) ₉ ) phosphate, butyl di- (4-CH ₃ (CH ₂ ) ₉ ) phosphate, butyl di- (5-CH ₃ (CH ₂ ) ₉ ) phosphate Pate, Butyl Di- (1-CH ₃ (CH ₂ ) ₁₀ ) Phosphate, Butyl Di- (2-CH ₃ (CH ₂ ) ₁₀ ) Phosphate, Butyl Di- (3-CH ₃ (CH ₂ ) ₁₀ ) Phosphate, Butyl di- (4-CH ₃ (CH ₂ ) ₁₀ ) phosphate, butyl di- (5-CH ₃ (CH ₂ ) ₁₀ ) phosphate, butyl di- (1-CH ₃ (CH ₂ ) ₁₁ ) phosphate, butyl di -(2-CH ₃ (CH ₂ ) ₁₁ ) phosphate, butyl di- (3-CH ₃ (CH ₂ ) ₁₁ ) phosphate, butyl di- (4-CH ₃ (CH ₂ ) ₁₁ ) phosphate, butyl di- ( 5-CH ₃ (CH ₂ ) ₁₁ ) phosphate, butyl di- (6-CH ₃ (CH ₂ ) ₁₁ ) phosphate, butyl di- (1-CH ₃ (CH ₂ ) ₁₂ ) phosphate, butyl di- (2- CH ₃ (CH ₂ ) ₁₂ ) phosphate, butyl di- (3-CH ₃ (CH ₂ ) ₁₂ ) phosphate, butyl di- (4-CH ₃ (CH ₂ ) ₁₂ ) phosphate, butyl di- (5-CH ₃ (CH _{2) 12)} phosphate, butyl di _{- (6-CH 3 (CH} 2) 12) phosphate, methyl ethyl propyl phosphate, methyl ethyl butyl phosphate, methyl ethyl pentyl phosphate, methyl ethyl hexyl phosphate, Methyl ethyl heptyl phosphate, 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 hexyl 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 hexyl 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 hexyl Phosphate, ethyl pentyl heptyl phosphate, ethyl pentyl octyl phosphate, ethyl hexyl heptyl phosphate, ethyl hexyl octyl phosphate, tri-phenyl 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, 1 octyl di-phenyl phosphate, 2 octyl di-phenyl phosphate, 3 octyl di-phenyl phosphate, 4 octyl di- Phenyl phosphate, 1 CH ₃ (CH ₂ ) ₈ di-phenyl phosphate, 2 CH ₃ (CH ₂ ) ₈ di-phenyl phosphate, 3 CH ₃ (CH ₂ ) ₈ di-phenyl phosphate, 4 CH ₃ (CH ₂ ) ₈ Di-phenyl phosphate, 1 CH ₃ (CH ₂ ) ₉ di-phenyl phosphate, 2 CH ₃ (CH ₂ ) ₉ di-phenyl phosphate, 3 CH ₃ (CH ₂ ) ₉ di-phenyl phosphate, 4 CH ₃ (CH ₂ ) ₉ di-phenyl phosphate, 5 CH ₃ (CH ₂ ) ₉ di-phenyl phosphate, 1 CH ₃ (CH ₂ ) ₁₀ di-phenyl phosphate, 2 CH ₃ (CH ₂ ) ₁₀ di-phenyl phosphate, 3 CH ₃ ( CH ₂ ) ₁₀ di-phenyl phosphate, 4 CH ₃ (CH ₂ ) ₁₀ di-phenyl phosphate, 5 CH ₃ (CH ₂ ) ₁₀ di-phenyl phosphate, 1 CH ₃ (CH ₂ ) ₁₁ di-phenyl phosphate, 2 CH ₃ (CH ₂ ) ₁₁ di-phenyl phosphate, 3 CH ₃ (CH ₂ ) ₁₁ di-phenyl phosphate, 4 CH ₃ (CH ₂ ) ₁₁ di-phenyl phosphate, 5 CH ₃ (CH ₂ ) ₁₁ di-phenyl phosphate, 6 CH ₃ (CH _{2) 11} di-phenyl _{phosphate, 1 CH 3 (CH 2)} 12 di-phenyl _{phosphate, 2 CH 3 (CH 2)} 12 -Phenyl _{phosphate, 3 CH 3 (CH 2)} 12 di-phenyl _{phosphate, 4 CH 3 (CH 2)} 12 di-phenyl _{phosphate, 5 CH 3 (CH 2)} 12 di-phenyl phosphate, 6 CH ₃ (CH _{2) 12} di-phenyl phosphate, di-methyl phenyl phosphate, di-ethyl 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- (l-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 Bit, di- (2-octyl) phenyl phosphate, di- (3-octyl) phenyl phosphate, di- (4-octyl) phenyl phosphate, di- (1-CH ₃ (CH _{2) 8)} phenyl phosphate, di- (2-CH ₃ (CH ₂ ) ₈ ) phenyl phosphate, di- (3-CH ₃ (CH ₂ ) ₈ ) phenyl phosphate, di- (4-CH ₃ (CH ₂ ) ₈ ) phenyl phosphate, di- (1 -CH ₃ (CH ₂ ) ₉ ) phenyl phosphate, di- (2-CH ₃ (CH ₂ ) ₉ ) phenyl phosphate, di- (3-CH ₃ (CH ₂ ) ₉ ) phenyl phosphate, di- (4-CH ₃ (CH ₂ ) ₉ ) phenyl phosphate, di- (5-CH ₃ (CH ₂ ) ₉ ) phenyl phosphate, di- (1-CH ₃ (CH ₂ ) ₁₀ ) phenyl phosphate, di- (2-CH ₃ ( CH ₂ ) ₁₀ ) phenyl phosphate, di- (3-CH ₃ (CH ₂ ) ₁₀ ) phenyl phosphate, di- (4-CH ₃ (CH ₂ ) ₁₀ ) phenyl phosphate, di- (5-CH ₃ (CH ₂₎ ) ₁₀ ) phenyl phosphate, di- (1-CH ₃ (CH ₂ ) ₁₁ ) phenyl phosphate, di- (2-CH ₃ (CH ₂ ) ₁₁ ) phenyl phosphate, di- (3-CH ₃ (CH ₂ ) ₁₁ ) Phenyl phosphate, di- (4-CH ₃ (CH ₂ ) ₁₁ ) phenyl phosphate, di- (5-CH ₃ (CH ₂ ) ₁₁ ) phenyl phosphate, di- (6-CH ₃ (CH ₂ ) ₁₁ ) phenyl phosphate, di- (1-CH ₃ (CH ₂ ) ₁₂ ) phenyl phosphate, di- (2 -CH ₃ (CH ₂ ) ₁₂ ) phenyl phosphate, di- (3-CH ₃ (CH ₂ ) ₁₂ ) phenyl phosphate, di- (4-CH ₃ (CH ₂ ) ₁₂ ) phenyl phosphate, di- (5-CH ₃ (CH ₂ ) ₁₂ ) phenyl phosphate, di- (6-CH ₃ (CH ₂ ) ₁₂ ) phenyl phosphate, tri-ethylene 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)) phosphate, Tri- (4- (1-butene)) phosphate, tri- (1- (2-butene)) phosphate, tri- (2- (2-butene)) phosphate, tri- (3- (2-butene)) Phosphate, tri- (4- (2-butene)) phosphate, tri- (1- (1-pentene)) phosphate, tri- (2- (1-pentene)) phosphate, tri- (3- (1-pentene) )) Phosphate, tri- (4- (1-pentene)) phosphate , Tri- (5- (1-pentene)) phosphate, tri- (1- (2-pentene)) phosphate, tri- (2- (2-pentene)) phosphate, tri- (3- (2-pentene) ) Phosphate, tri- (4- (2-pentene)) phosphate, tri- (5- (2-pentene)) phosphate, tri- (1- (1-hexene)) phosphate, tri- (2-(1 -Hexene)) phosphate, tri- (3- (1-hexene)) phosphate, tri- (4- (1-hexene)) phosphate, tri- (5- (1-hexene)) phosphate, tri- (6- (1-hexene)) phosphate, tri- (1- (3-hexene)) phosphate, tri- (2- (3-hexene)) phosphate, tri- (3- (3-hexene)) phosphate, tri- ( 4- (3-hexene)) phosphate, tri- (5- (3-hexene)) phosphate, tri- (6- (3-hexene)) phosphate, tri- (1- (2-hexene)) phosphate, tree -(2- (2-hexene)) phosphate, tri- (3- (2-hexene)) phosphate, tri- (4- (2-hexene)) phosphate, tri- (5- (2-hexene)) phosphate , Tri- (6- (2-hexene)) phosphate, tri- (phenyl methyl) phosphate, tri- (2-methyl Nil) phosphate, tri- (3-methyl phenyl) phosphate, tri- (4-methyl phenyl) phosphate, tri- (2-ethyl phenyl) phosphate, tri- (3-ethyl phenyl) phosphate and tri- (4-ethyl Phenyl) phosphate.
[90] Specific examples of di-phosphates include the following:
[91] Di-methyl phosphate, di-ethyl 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- (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, di- (1-CH ₃ (CH ₂ ) ₈ ) phosphate, di- (2-CH ₃ (CH ₂ ) ₈ ) phosphate, di- (3-CH ₃ (CH ₂ ) ₈ ) phosphate, di- (4-CH ₃ (CH ₂ ) ₈ ) phosphate, di- (1-CH ₃ (CH ₂ ) ₉ ) phosphate, di- (2-CH ₃ (CH ₂ ) ₉ ) phosphate, di- (3-CH ₃ (CH ₂ ) ₉ ) phosphate, di -(4-CH ₃ (CH ₂ ) ₉ ) phosphate, di- (5-CH ₃ (CH ₂ ) ₉ ) phosphate, di- (1-CH ₃ (CH ₂ ) ₁₀ ) phosphate, di- (2-CH ₃ (CH ₂ ) ₁₀ ) phosphate, di- (3-CH ₃ (CH ₂ ) ₁₀ ) phosphate, di- (4-CH ₃ (CH ₂ ) ₁₀ ) phosphate, di- (5-CH ₃ (CH ₂ ) ₁₀ ) phosphate, di- (1-CH ₃ (CH ₂ ) ₁₁ ) phosphate, di- (2-CH ₃ (CH ₂ ) ₁₁ ) phosphate, di- (3-CH ₃ (CH ₂ ) ₁₁ ) phosphate, di -(4-CH ₃ (CH ₂ ) ₁₁ ) phosphate, di- (5-CH ₃ (CH ₂ ) ₁₁ ) phosphate, di- (6-CH ₃ (CH ₂ ) ₁₁ ) phosphate, di- (1-CH ₃ (CH ₂ ) ₁₂ ) phosphate, di- (2-CH ₃ (CH ₂ ) ₁₂ ) phosphate, di- (3-CH ₃ (CH ₂ ) ₁₂ ) phosphate, di- (4-CH ₃ (CH ₂ ) ₁₂ ) phosphate, di- (5-CH ₃ (CH ₂ ) ₁₂ ) phosphate, di- (6-CH ₃ (CH ₂ ) ₁₂ ) phosphate, di- (1- (methyl pentyl)) phosphate, di- (2 -(Methyl pentyl)) phosphate, di- (3- (methyl pentyl)) phosphate, di- (1- (di-methyl pentyl)) phosphate, di- (2- (di-methyl pentyl)) phosphate , Di- (3- (di-methyl pentyl)) phosphate, di- (1- (ethyl pentyl)) phosphate, di- (2- (ethyl pentyl)) phosphate, di- (3- (ethyl pentyl)) Phosphate, di- (1- (methyl hexyl)) phosphate, di- (2- (methyl hexyl)) phosphate, di- (3- (methyl hexyl)) phosphate, di- (1- (di-methyl hexyl)) Phosphate, di- (2- (di-methyl hexyl)) phosphate, di- (3- (di-methyl hexyl)) phosphate, di- (1- (ethyl hexyl)) phosphate, di- (2- (ethyl hexyl) )) Phosphate, di- (3- (ethyl hexyl)) phosphate, di- (methyl heptyl) phosphate, di- (di-methyl heptyl) phosphate, di- (ethyl heptyl) phosphate, di- (methyl octyl) phosphate, Di- (di-methyl octyl) phosphate, di- (ethyl octyl) phosphate, methyl ethyl phosphate, methyl propyl phosphate, methyl butyl phosphate, methyl tert-butyl phosphate, methyl pentyl phosphate, methyl hexyl phosphate, methyl heptyl phosphate Sites, methyl octyl phosphate, methyl CH ₃ (CH _{2) 8} phosphate, methyl CH ₃ (CH _{2) 9} phosphate, methyl CH ₃ (CH _{2) 10} phosphate, methyl CH ₃ (CH _{2) 11} phosphate, methyl CH ₃ ( CH ₂ ) ₁₂ phosphate, ethyl propyl phosphate, ethyl butyl phosphate, ethyl tert-butyl phosphate, ethyl pentyl phosphate, ethyl hexyl phosphate, ethyl heptyl phosphate, ethyl octyl phosphate, ethyl CH ₃ (CH ₂ ) ₈ phosphate, ethyl CH ₃ (CH ₂ ) ₉ phosphate, ethyl CH ₃ (CH ₂ ) ₁₀ phosphate, ethyl CH ₃ (CH ₂ ) ₁₁ phosphate, ethyl CH ₃ (CH ₂ ) ₁₂ phosphate, propyl butyl phosphate, propyl tert-butyl phosphate, propyl Pentyl phosphate, propyl hexyl phosphate, propyl heptyl phosphate, propyl octyl phosphate, propyl CH ₃ (CH ₂ ) ₈ phosphate, propyl CH ₃ (CH ₂ ) ₉ phosphate, propyl CH ₃ (CH ₂ ) ₁₀ phosphate, fr Lofil CH ₃ (CH ₂ ) ₁₁ phosphate, propyl CH ₃ (CH ₂ ) ₁₂ phosphate, butyl tert-butyl phosphate, tert-butyl pentyl phosphate, tert-butyl hexyl phosphate, tert-butyl heptyl phosphate, tertiary -Butyl octyl phosphate, tert-butyl CH ₃ (CH ₂ ) ₈ phosphate, tert-butyl CH ₃ (CH ₂ ) ₉ phosphate, tert-butyl CH ₃ (CH ₂ ) ₁₀ phosphate, tert-butyl CH ₃ (CH ₂ ) ₁₁ phosphate, tert-butyl CH ₃ (CH ₂ ) ₁₂ phosphate, pentyl hexyl phosphate, pentyl heptyl phosphate, pentyl octyl phosphate, pentyl CH ₃ (CH ₂ ) ₈ phosphate, pentyl CH ₃ (CH ₂ ) ₉ Phosphate, pentyl CH ₃ (CH ₂ ) ₁₀ phosphate, pentyl CH ₃ (CH ₂ ) ₁₁ phosphate, pentyl CH ₃ (CH ₂ ) ₁₂ phosphate, hexyl heptyl phosphate, heptyl octyl phosphate, hexyl CH ₃ (CH ₂ ) ₈ phosphate, Hexyl CH ₃ (CH ₂ ) ₉ phosphate, hexyl CH ₃ (CH ₂ ) ₁₀ phosphate, hexyl CH ₃ (CH ₂ ) ₁₁ phosphate, hex Real CH ₃ (CH ₂ ) ₁₂ phosphate, di-butene phosphate, di-pentene phosphate, di-hexene phosphate, di-heptene phosphate and di-octene phosphate.
[92] Specific examples of mono-phosphates are as follows:
[93] Methyl phosphate, ethyl phosphate, propyl phosphate, butyl phosphate, pentyl phosphate, hexyl phosphate, heptyl phosphate, octyl phosphate, CH ₃ (CH ₂ ) ₈ phosphate, CH ₃ (CH ₂ ) ₉ phosphate, CH ₃ (CH ₂ ) ₁₀ phosphate , CH ₃ (CH ₂ ) ₁₁ phosphate, CH ₃ (CH ₂ ) ₁₂ phosphate, methyl propyl phosphate, methyl butyl phosphate, methyl pentyl phosphate, methyl hexyl phosphate, methyl heptyl phosphate, methyl octyl phosphate, methyl CH ₃ (CH ₂ ) ₈ phosphate, methyl CH ₃ (CH ₂ ) ₉ phosphate, methyl CH ₃ (CH ₂ ) ₁₀ phosphate, methyl CH ₃ (CH ₂ ) ₁₁ phosphate, methyl CH ₃ (CH ₂ ) ₁₂ phosphate, di-methyl butyl phosphate, di -methyl pentyl phosphate, di-methyl hexyl phosphate, di-methyl heptyl phosphate, di-methyl octyl phosphate, di-methyl CH ₃ (CH _{2) 8} phosphate, di-methyl CH ₃ (CH _{2) 9} force Fe Agent, di-methyl CH ₃ (CH _{2) 10} phosphate, di-methyl CH ₃ (CH _{2) 11} phosphate, di-methyl CH ₃ (CH _{2) 12} phosphate, ethyl butyl phosphate, ethyl pentyl phosphate, ethyl hexyl phosphate, Ethyl heptyl phosphate, ethyl octyl phosphate, ethyl CH ₃ (CH ₂ ) ₈ phosphate, ethyl CH ₃ (CH ₂ ) ₉ phosphate, ethyl CH ₃ (CH ₂ ) ₁₀ phosphate, ethyl CH ₃ (CH ₂ ) ₁₁ phosphate, ethyl CH ₃ (CH ₂ ) ₁₂ phosphate, butene phosphate, pentene phosphate, hexene phosphate, heptene phosphate and octene phosphate.
[94] For brevity, no list of phosphites is provided; However, the species of applicable phosphites correspond to the tri, di and mono phosphates provided in the preceding paragraphs. For example, by simply repeating "phosphate" as "phosphite" in the preceding paragraph, one can quickly generate a list of representative phosphite species applicable to the present invention.
[95] Examples of phosphine compounds are as follows:
[96] 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-CH ₃ (CH ₂ ) ₈ ) phosphine, tri- (2-CH ₃ (CH ₂ ) ₈ ) phosphine, tri- (3-CH ₃ ( CH ₂ ) ₈ ) phosphine, tri- (4-CH ₃ (CH ₂ ) ₈ ) phosphine, tri- (1-CH ₃ (CH ₂ ) ₉ ) phosphine, tri- (2-CH ₃ (CH ₂₎ ) ₉ ) phosphine, tri- (3-CH ₃ (CH ₂ ) ₉ ) phosphine, tri- (4-CH ₃ (CH ₂ ) ₉ ) phosphine, tri- (5-CH ₃ (CH ₂ ) ₉ ) Phosphine, tri- (1-CH ₃ (CH ₂ ) ₁₀ ) phosphine, tri- (2-CH ₃ (CH ₂ ) ₁₀ ) phosphine, tri- (3-CH ₃ (CH ₂ ) ₁₀ ) phosphine Pin, tri- (4-CH ₃ (CH ₂ ) ₁₀ ) phosphine, tri- (5-CH ₃ (CH ₂ ) ₁₀ ) phosphine, tri- (1-CH ₃ (CH ₂ ) ₁₁ ) phosphine, Tri- (2-CH ₃ (CH ₂ ) ₁₁ ) phosphine, tri- (3-CH ₃ (CH ₂ ) ₁₁ ) phosphine, tri- (4-CH ₃ (CH ₂ ) ₁₁ ) Phosphine, tri- (5-CH ₃ (CH ₂ ) ₁₁ ) phosphine, tri- (6-CH ₃ (CH ₂ ) ₁₁ ) phosphine, tri- (1-CH ₃ (CH ₂ ) ₁₂ ) phosphine , Tri- (2-CH ₃ (CH ₂ ) ₁₂ ) phosphine, tri- (3-CH ₃ (CH ₂ ) ₁₂ ) phosphine, tri- (4-CH ₃ (CH ₂ ) ₁₂ ) phosphine, tree -(5-CH ₃ (CH ₂ ) ₁₂ ) phosphine, tri- (6-CH ₃ (CH ₂ ) 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 Pin, methyl di- (1-CH ₃ (CH ₂ ) ₈ ) phosphine, methyl di- (2-CH ₃ (CH ₂ ) ₈ ) phosphine, methyl di- (3-CH ₃ (CH ₂ ) ₈ ) Phosphine, methyl di- (4-CH ₃ (CH ₂ ) ₈ ) phosphine, methyl di- (1-CH ₃ (CH ₂ ) ₉ ) phosphine, methyl di- (2-CH ₃ (CH ₂ ) ₉ ) Phosphine, methyl di- (3-CH ₃ (CH ₂ ) ₉ ) phosphine, methyl di- (4-CH ₃ ( CH ₂ ) ₉ ) phosphine, methyl di- (5-CH ₃ (CH ₂ ) ₉ ) phosphine, methyl di- (1-CH ₃ (CH ₂ ) ₁₀ ) phosphine, methyl di- (2-CH ₃ (CH ₂ ) ₁₀ ) phosphine, methyl di- (3-CH ₃ (CH ₂ ) ₁₀ ) phosphine, methyl di- (4-CH ₃ (CH ₂ ) ₁₀ ) phosphine, methyl di- (5-CH ₃ (CH ₂ ) ₁₀ ) phosphine, methyl di- (1-CH ₃ (CH ₂ ) ₁₁ ) phosphine, methyl di- (2-CH ₃ (CH ₂ ) ₁₁ ) phosphine, methyl di- (3- CH ₃ (CH ₂ ) ₁₁ ) phosphine, methyl di- (4-CH ₃ (CH ₂ ) ₁₁ ) phosphine, methyl di- (5-CH ₃ (CH ₂ ) ₁₁ ) phosphine, methyl di- (6 -CH ₃ (CH ₂ ) ₁₁ ) phosphine, methyl di- (1-CH ₃ (CH ₂ ) ₁₂ ) phosphine, methyl di- (2-CH ₃ (CH ₂ ) ₁₂ ) phosphine, methyl di- ( 3-CH ₃ (CH ₂ ) ₁₂ ) phosphine, methyl di- (4-CH ₃ (CH ₂ ) ₁₂ ) phosphine, methyl di- (5-CH ₃ (CH ₂ ) ₁₂ ) phosphine, methyl di- (6-CH ₃ (CH ₂ ) ₁₂ ) phosphine, ethyl di- (1-hexyl) phosphine, ethyl di- (2-hexyl) phosphine, ethyl di- (3-hexyl) phosphine, ethyl di- (1-heptyl) phosphine, ethyl di- (2-heptyl) phosphine, ethyl di- (3-heptyl) phosphine, ethyl -(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-CH ₃ (CH ₂ ) ₈ ) phosphine, ethyl di- (2-CH ₃ (CH ₂ ) ₈ ) phosphine, ethyl di- (3-CH ₃ (CH ₂ ) ₈ ) Phosphine, ethyl di- (4-CH ₃ (CH ₂ ) ₈ ) phosphine, ethyl di- (1-CH ₃ (CH ₂ ) ₉ ) phosphine, ethyl di- (2-CH ₃ (CH ₂ ) ₉ ) phosphine, ethyl di- (3-CH ₃ (CH ₂ ) ₉ ) phosphine, ethyl di- (4-CH ₃ (CH ₂ ) ₉ ) phosphine, ethyl di- (5-CH ₃ (CH ₂₎ ) ₉ ) phosphine, ethyl di- (1-CH ₃ (CH ₂ ) ₁₀ ) phosphine, ethyl di- (2-CH ₃ (CH ₂ ) ₁₀ ) phosphine, ethyl di- (3-CH ₃ (CH ₂ ) ₁₀ ) phosphine, ethyl di- (4-CH ₃ (CH ₂ ) ₁₀ ) phosphine, ethyl di- (5-CH ₃ (CH ₂ ) ₁₀ ) phosphine, ethyl di- (1-CH ₃ ( CH ₂ ) ₁₁ ) phosphine, ethyl di- (2-CH ₃ (CH ₂ ) ₁₁ ) phosphine, ethyl di- (3-CH ₃ (CH ₂ ) ₁₁ ) phosphine, ethyl di- (4-CH ₃ (CH ₂ ) ₁₁ ) phosphine, ethyl di- (5-CH ₃ (CH ₂ ) ₁₁ ) phosphine, ethyl di- (6-CH ₃ (CH ₂ ) ₁₁ ) foam Spin, ethyl di- (1-CH ₃ (CH ₂ ) ₁₂ ) phosphine, ethyl di- (2-CH ₃ (CH ₂ ) ₁₂ ) phosphine, ethyl di- (3-CH ₃ (CH ₂ ) ₁₂ ) Phosphine, ethyl di- (4-CH ₃ (CH ₂ ) ₁₂ ) phosphine, ethyl di- (5-CH ₃ (CH ₂ ) ₁₂ ) phosphine, ethyl di- (6-CH ₃ (CH ₂ ) 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-CH ₃ (CH ₂ ) ₈ ) phosphine, 1-propyl di- (2-CH ₃ (CH ₂ ) ₈ ) phosphine, 1-propyl di- (3-CH ₃ (CH ₂ ) ₈ ) Phosphine, 1-propyl di- (4-CH ₃ (CH ₂ ) ₈ ) phosphine, 1-propyl di- (1-CH ₃ (CH ₂ ) ₉ ) phosphine, 1-propyl di- (2- CH ₃ (CH ₂ ) ₉ ) phosphine, 1-propyl di- (3-CH ₃ (CH ₂ ) ₉ ) Phosphine, 1-propyl di- (4-CH ₃ (CH ₂ ) ₉ ) phosphine, 1-propyl di- (5-CH ₃ (CH ₂ ) ₉ ) phosphine, 1-propyl di- (1- CH ₃ (CH ₂ ) ₁₀ ) phosphine, 1-propyl di- (2-CH ₃ (CH ₂ ) ₁₀ ) phosphine, 1-propyl di- (3-CH ₃ (CH ₂ ) ₁₀ ) phosphine, 1 -Propyl di- (4-CH ₃ (CH ₂ ) ₁₀ ) phosphine, 1-propyl di- (5-CH ₃ (CH ₂ ) ₁₀ ) phosphine, 1-propyl di- (1-CH ₃ (CH ₂₎ ) ₁₁ ) phosphine, 1-propyl di- (2-CH ₃ (CH ₂ ) ₁₁ ) phosphine, 1-propyl di- (3-CH ₃ (CH ₂ ) ₁₁ ) phosphine, 1-propyl di- ( 4-CH ₃ (CH ₂ ) ₁₁ ) phosphine, 1-propyl di- (5-CH ₃ (CH ₂ ) ₁₁ ) phosphine, 1-propyl di- (6-CH ₃ (CH ₂ ) ₁₁ ) phosphine , 1-propyl di- (1-CH ₃ (CH ₂ ) ₁₂ ) phosphine, 1-propyl di- (2-CH ₃ (CH ₂ ) ₁₂ ) phosphine, 1-propyl di- (3-CH ₃ ( CH ₂ ) ₁₂ ) phosphine, 1-propyl di- (4-CH ₃ (CH ₂ ) ₁₂ ) phosphine, 1-propyl di- (5-CH ₃ (CH ₂ ) ₁₂ ) phosphine, 1-propyl di -(6-CH ₃ (CH ₂ ) ₁₂ ) phosphine, 2-propyl di- (1-hexyl) phosphine, 2-propyl di- (2-hexyl) phosphine, 2 -Propyl di- (3-hexyl) phosphine, 2-propyl di- (1-heptyl) phosphine, 2-propyl di- (2-heptyl) phosphine, 2-propyl di- (3-heptyl) phosphine , 2-propyl di- (4-heptyl) phosphine, 2-propyl di- (1-octyl) phosphine, 2-propyl di- (2-octyl) phosphine, 2-propyl di- (3-octyl) Phosphine, 2-propyl di- (4-octyl) phosphine, 2-propyl di- (1-CH ₃ (CH ₂ ) ₈ ) phosphine, 2-propyl di- (2-CH ₃ (CH ₂ ) ₈ ) Phosphine, 2-propyl di- (3-CH ₃ (CH ₂ ) ₈ ) phosphine, 2-propyl di- (4-CH ₃ (CH ₂ ) ₈ ) phosphine, 2-propyl di- (1- CH ₃ (CH ₂ ) ₉ ) phosphine, 2-propyl di- (2-CH ₃ (CH ₂ ) ₉ ) phosphine, 2-propyl di- (3-CH ₃ (CH ₂ ) ₉ ) phosphine, 2 -Propyl di- (4-CH ₃ (CH ₂ ) ₉ ) phosphine, 2-propyl di- (5-CH ₃ (CH ₂ ) ₉ ) phosphine, 2-propyl di- (1-CH ₃ (CH ₂₎ ) ₁₀ ) phosphine, 2-propyl di- (2-CH ₃ (CH ₂ ) ₁₀ ) phosphine, 2-propyl di- (3-CH ₃ (CH ₂ ) ₁₀ ) phosphine, 2-propyl di- ( _{4-CH 3 (CH 2)} 10) phosphine, 2-propyl di _{- (5-CH 3 (CH} 2) 10) phosphine , 2-propyl di _{- (1-CH 3 (CH} 2) 11) phosphine, 2-propyl di _{- (2-CH 3 (CH} 2) 11) phosphine, 2-propyl di - _(3-CH 3 ( CH ₂ ) ₁₁ ) phosphine, 2-propyl di- (4-CH ₃ (CH ₂ ) ₁₁ ) phosphine, 2-propyl di- (5-CH ₃ (CH ₂ ) ₁₁ ) phosphine, 2-propyl di -(6-CH ₃ (CH ₂ ) ₁₁ ) phosphine, 2-propyl di- (1-CH ₃ (CH ₂ ) ₁₂ ) phosphine, 2-propyl di- (2-CH ₃ (CH ₂ ) ₁₂ ) Phosphine, 2-propyl di- (3-CH ₃ (CH ₂ ) ₁₂ ) phosphine, 2-propyl di- (4-CH ₃ (CH ₂ ) ₁₂ ) phosphine, 2-propyl di- (5-CH ₃ (CH ₂ ) ₁₂ ) phosphine, 2-propyl di- (6-CH ₃ (CH ₂ ) ₁₂ ) phosphine, butyl di- (1-hexyl) phosphine, butyl di- (2-hexyl) phosphine , Butyl di- (3-hexyl) phosphine, butyl di- (1-heptyl) phosphine, butyl di- (2-heptyl) phosphine, butyl di- (3-heptyl) phosphine, butyl di- (4 -Heptyl) phosphine, butyl di- (1-octyl) phosphine, butyldi- (2-octyl) phosphine, butyl di- (3-octyl) phosphine, butyl di- (4-octyl) phosphine, Butyl di- (1-CH ₃ (CH ₂ ) ₈ ) phosphine, butyl di- (2-CH ₃ (CH ₂ ) ₈ ) phosphine, butyl di- (3-CH ₃ (CH ₂ ) ₈ ) phosphine, butyl di- (4-CH ₃ (CH ₂ ) ₈ ) phosphine, butyl di- (1- CH ₃ (CH ₂ ) ₉ ) phosphine, butyl di- (2-CH ₃ (CH ₂ ) ₉ ) phosphine, butyl di- (3-CH ₃ (CH ₂ ) ₉ ) phosphine, butyl di- (4 -CH ₃ (CH ₂ ) ₉ ) phosphine, butyl di- (5-CH ₃ (CH ₂ ) ₉ ) phosphine, butyl di- (1-CH ₃ (CH ₂ ) ₁₀ ) phosphine, butyl di- ( 2-CH ₃ (CH ₂ ) ₁₀ ) phosphine, butyl di- (3-CH ₃ (CH ₂ ) ₁₀ ) phosphine, butyl di- (4-CH ₃ (CH ₂ ) ₁₀ ) phosphine, butyl di- (5-CH ₃ (CH ₂ ) ₁₀ ) phosphine, butyl di- (1-CH ₃ (CH ₂ ) ₁₁ ) phosphine, butyl di- (2-CH ₃ (CH ₂ ) ₁₁ ) phosphine, butyl di -(3-CH ₃ (CH ₂ ) ₁₁ ) phosphine, butyl di- (4-CH ₃ (CH ₂ ) ₁₁ ) phosphine, butyl di- (5-CH ₃ (CH ₂ ) ₁₁ ) phosphine, butyl Di- (6-CH ₃ (CH ₂ ) ₁₁ ) phosphine, butyl di- (1-CH ₃ (CH ₂ ) ₁₂ ) phosphine, butyl di- (2-CH ₃ (CH ₂ ) ₁₂ ) phosphine, butyl di _{- (3-CH 3 (CH} 2) 12) phosphine, butyl di _{- (4-CH 3 (CH} 2) 12) phosphine, butyl di _{- (5-CH 3 (CH} 2) 12) PO Pin, butyl di _{- (6-CH 3 (CH} 2) 12) phosphine, methyl hexyl heptyl phosphine, methyl hexyl octyl phosphine, ethyl propyl butyl phosphine, ethyl propyl pentyl phosphine, ethyl propyl hexyl phosphine, ethyl Propyl heptyl phosphine, ethyl propyl octyl phosphine, ethyl butyl pentyl phosphine, ethyl butyl hexyl phosphine, ethyl butyl heptyl phosphine, ethyl butyl octyl phosphine, ethyl pentyl hexyl phosphine, ethyl pentyl heptyl phosphine, ethyl pentyl octyl Phosphine, ethyl hexyl heptyl phosphine, ethyl hexyl octyl phosphine, tri-phenyl phosphine, 1 hexyl di-phenyl phosphine, 2 hexyl di-phenyl phosphine, 3 hexyl di-phenyl phosphine, 1 heptyl di-phenyl Phosphine, 2 heptyl di-phenyl phosphine, 3 heptyl di-phenyl phosphine, 4 heptyl di-phenyl phosphine, 1 octyl di-phenyl phosphine, 2 octyl di-phenyl phosphine, 3 octyl di-phenyl phosphine , 4 octyl di-phenyl _{phosphine, 1 CH 3 (CH 2)} 8 di-phenyl _{phosphine, 2 CH 3 (CH 2)} 8 -Phenyl _{phosphine, 3 CH 3 (CH 2)} 8 di-phenyl _{phosphine, 4 CH 3 (CH 2)} 8 di-phenyl _{phosphine, 1 CH 3 (CH 2)} 9 di-phenyl phosphine, 2 CH ₃ (CH ₂ ) ₉ di-phenyl phosphine, 3 CH ₃ (CH ₂ ) ₉ di-phenyl phosphine, 4 CH ₃ (CH ₂ ) ₉ di-phenyl phosphine, 5 CH ₃ (CH ₂ ) ₉ di-phenyl Phosphine, 1 CH ₃ (CH ₂ ) ₁₀ di-phenyl phosphine, 2 CH ₃ (CH ₂ ) ₁₀ di-phenyl phosphine, 3 CH ₃ (CH ₂ ) ₁₀ di-phenyl phosphine, 4 CH ₃ (CH ₂ ) ₁₀ di-phenyl phosphine, 5 CH ₃ (CH ₂ ) ₁₀ di-phenyl phosphine, 1 CH ₃ (CH ₂ ) ₁₁ di-phenyl phosphine, 2 CH ₃ (CH ₂ ) ₁₁ di-phenyl phosphine , 3 CH ₃ (CH ₂ ) ₁₁ di-phenyl phosphine, 4 CH ₃ (CH ₂ ) ₁₁ di-phenyl phosphine, 5 CH ₃ (CH ₂ ) ₁₁ di-phenyl phosphine, 6 CH ₃ (CH ₂ ) ₁₁ di-phenyl phosphine, 1 CH ₃ (CH ₂ ) ₁₂ di-phenyl phosphine, 2 CH ₃ (CH ₂ ) ₁₂ di-phenyl phosphine, 3 CH ₃ (CH ₂ ) ₁₂ di-phenyl phosphine, 4 CH ₃ (CH _{2) 12} di-phenyl _{phosphine, 5 CH 3 (CH 2)} 12 di-phenyl _{phosphine, 6 CH 3 (CH 2)} 12 di-phenyl phosphine, di- (1-hexyl) phenyl PO Pin, di- (2-hexyl) phenyl phosphine, di- (3-hexyl) phenyl phosphine, di- (1-heptyl) phenyl phosphine, di- (2-heptyl) phenyl phosphine, di- (3 -Heptyl) phenyl phosphine, di- (4-heptyl) phenyl phosphine, di- (1-octyl) phenyl phosphine, di- (2-octyl) phenyl phosphine, di- (3-octyl) phenyl phosphine , Di- (4-octyl) phenyl phosphine, di- (1-CH ₃ (CH ₂ ) ₈ ) phenyl phosphine, di- (2-CH ₃ (CH ₂ ) ₈ ) phenyl phosphine, di- (3 -CH ₃ (CH ₂ ) ₈ ) phenyl phosphine, di- (4-CH ₃ (CH ₂ ) ₈ ) phenyl phosphine, di- (1-CH ₃ (CH ₂ ) ₉ ) phenyl phosphine, di- ( 2-CH ₃ (CH ₂ ) ₉ ) phenyl phosphine, di- (3-CH ₃ (CH ₂ ) ₉ ) phenyl phosphine, di- (4-CH ₃ (CH ₂ ) ₉ ) phenyl phosphine, di- (5-CH ₃ (CH ₂ ) ₉ ) phenyl phosphine, di- (1-CH ₃ (CH ₂ ) ₁₀ ) phenyl phosphine, di- (2-CH ₃ (CH ₂ ) ₁₀ ) phenyl phosphine, di -(3-CH ₃ (CH ₂ ) ₁₀ ) phenyl phosphine, di- (4-CH ₃ (CH ₂ ) ₁₀ ) phenyl phosphine, di- (5-CH ₃ (CH ₂ ) ₁₀ ) phenyl phosphine, di _{- (1-CH 3 (CH} 2) 11) phenyl phosphine, di _{- (2-CH 3 (CH} 2) 11) Carbonyl phosphine, di _{- (3-CH 3 (CH} 2) 11) phenyl phosphine, di _{- (4-CH 3 (CH} 2) 11) phenyl phosphine, di _{- (5-CH 3 (CH} 2) 11 ) Phenyl phosphine, di- (6-CH ₃ (CH ₂ ) ₁₁ ) phenyl phosphine, di- (1-CH ₃ (CH ₂ ) ₁₂ ) phenyl phosphine, di- (2-CH ₃ (CH ₂ ) ₁₂ ) Phenyl phosphine, di- (3-CH ₃ (CH ₂ ) ₁₂ ) Phenyl phosphine, di- (4-CH ₃ (CH ₂ ) ₁₂ ) Phenyl phosphine, di- (5-CH ₃ (CH ₂₎ ) ₁₂ ) phenyl phosphine, di- (6-CH ₃ (CH ₂ ) ₁₂ ) phenyl phosphine, tri- (phenyl methyl) phosphine, tri- (2-methyl phenyl) phosphine, tri- (3-methyl Phenyl) phosphine, tri- (4-methyl phenyl) phosphine, tri- (2-ethyl phenyl) phosphine, tri- (3-ethyl phenyl) phosphine, tri- (4-ethyl phenyl) phosphine, tri -(Hexene) phosphine, tri- (heptene) phosphine, tri- (octene) phosphine and tri- (heptyl) phosphine.
[97] Examples of phosphine oxides each correspond to the phosphines described above. A list of such oxides can be generated quickly by simply adding "oxides" to each of the phosphine species described above.
[98] Examples of di-phosphonates are as follows:
[99] Tetra-methyl di-phosphonate, tetra-ethyl di-phosphonate, tetra- (1-propyl) di-phosphonate, tetra- (2-propyl) di-phosphonate, tetra- (1-butyl ) Di-phosphonate, tetra- (2-butyl) di-phosphonate, tetra- (l-tert-butyl) di-phosphonate, tetra- (2-tert-butyl) di-phospho Nate, tetra- (1-pentyl) di-phosphonate, tetra- (2-pentyl) di-phosphonate, tetra- (3-pentyl) di-phosphonate, tetra- (1-hexyl) di- Phosphonate, tetra- (2-hexyl) di-phosphonate, tetra- (3-hexyl) di-phosphonate, tetra- (1-heptyl) di-phosphonate, tetra- (2-heptyl) Di-phosphonate, tetra- (3-heptyl) di-phosphonate, tetra- (4-heptyl) di-phosphonate, tetra- (1-octyl) di-phosphonate, tetra- (2- Octyl) di-phosphonate, tetra- (3-octyl) di-phosphonate, tetra- (4-octyl) di-phosphonate, Trad _{- (1-CH 3 (CH} 2) 8) di-phosphonate, tetra _{- (2-CH 3 (CH} 2) 8) di-phosphonate, tetra _{- (3-CH 3 (CH} 2) 8 ) Di-phosphonate, tetra- (4-CH ₃ (CH ₂ ) ₈ ) di-phosphonate, tetra- (1-CH ₃ (CH ₂ ) ₉ ) di-phosphonate, tetra- (2- CH ₃ (CH ₂ ) ₉ ) di-phosphonate, tetra- (3-CH ₃ (CH ₂ ) ₉ ) di-phosphonate, tetra- (4-CH ₃ (CH ₂ ) ₉ ) di-phospho Nate, tetra- (5-CH ₃ (CH ₂ ) ₉ ) di-phosphonate, tetra- (1-CH ₃ (CH ₂ ) ₁₀ ) di-phosphonate, tetra- (2-CH ₃ (CH ₂₎ ) ₁₀ ) di-phosphonate, tetra- (3-CH ₃ (CH ₂ ) ₁₀ ) di-phosphonate, tetra- (4-CH ₃ (CH ₂ ) ₁₀ ) di-phosphonate, tetra- ( 5-CH ₃ (CH ₂ ) ₁₀ ) di-phosphonate, tetra- (1-CH ₃ (CH ₂ ) ₁₁ ) di-phosphonate, tetra- (2-CH ₃ (CH ₂ ) ₁₁ ) di- Phosphonate, tetra- (3-CH ₃ (CH ₂ ) ₁₁ ) di-phosphonate, tetra- (4-CH ₃ (CH ₂ ) ₁₁ ) di-phosphonate, tetra- (5-CH ₃ ( CH ₂ ) ₁₁ ) di-phosphonate, tetra- (6-CH ₃ (CH ₂ ) ₁₁ ) di-phosphonate, tetra- (1-CH ₃ (CH ₂ ) ₁₂ ) di-phosphonate, tetra- (2-CH ₃ (CH ₂ ) ₁₂ ) di-phosphonate, tetra- (3-CH ₃ (CH ₂ ) ₁₂ ) di-phosphonate, tetra- (4-CH ₃ (CH ₂ ) ₁₂ ) di -Phosphonate, tetra- (5-CH ₃ (CH ₂ ) ₁₂ ) di-phosphonate, tetra- (6-CH ₃ (CH ₂ ) ₁₂ ) di-phosphonate, tetra-phenyl di-phospho , Di-methyl- (di-ethyl) di-phosphonate, di-methyl- (di-phenyl) di-phosphonate and di-methyl- (di-4-pentene) di-phosphonate.
[100] Examples of pyrophosphate compounds are as follows:
[101] Tetra-methyl pyrophosphate, tetra-ethyl pyrophosphate, tetra- (1-propyl) pyrophosphate, tetra- (2-propyl) pyrophosphate, tetra- (1-butyl) pyrophosphate, tetra- (2-butyl) fatigue Phosphate, tetra- (l-tert-butyl) pyrophosphate, tetra- (l-tert-butyl) pyrophosphate, tetra- (l-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, tetra- (3-heptyl) pyrophosphate, tetra- (4-heptyl) pyrophosphate, tetra- (1-octyl) pyrophosphate, tetra- (2-octyl) pyrophosphate, tetra- (3-octyl) pyrophosphate, tetra- (4-octyl) pyrophosphate, tetra- (1-CH ₃ (CH ₂₎ ) ₈ ) pyrophosphate, tetra- (2-CH ₃ (CH ₂ ) ₈ ) pyrophosphate, tetra- (3-CH ₃ (CH ₂ ) ₈ ) pyrophosphate, tetra- (4-CH ₃ (CH ₂ ) ₈ ) Pyrophosphate, tetra- (1-CH ₃ (CH ₂ ) ₉ ) pyrophosphate, tetra- (2-CH ₃ (CH ₂ ) ₉ ) pyrophosphate, tetra- (3-CH ₃ (CH ₂ ) ₉ ) fatigue Phosphate, tetra- (4-CH ₃ (CH ₂ ) ₉ ) pyrophosphate, tetra- (5-CH ₃ (CH ₂ ) ₉ ) pyrophosphate, tetra- (1-CH ₃ (CH ₂ ) ₁₀ ) pyrophosphate, Tetra- (2-CH ₃ (CH ₂ ) ₁₀ ) pyrophosphate, tetra- (3-CH ₃ (CH ₂ ) ₁₀ ) pyrophosphate, tetra- (4-CH ₃ (CH ₂ ) ₁₀ ) pyrophosphate, tetra- (5-CH ₃ (CH ₂ ) ₁₀ ) pyrophosphate, tetra- (1-CH ₃ (CH ₂ ) ₁₁ ) pyrophosphate, tetra- (2-CH ₃ (CH ₂ ) ₁₁ ) pyrophosphate, tetra- (3 -CH ₃ (CH _{2) 11)} pyrophosphate, tetra _{- (4-CH 3 (CH} 2) 11) pyrophosphate, tetra _{- (5-CH 3 (CH} 2) 11) pyrophosphate, Tet _{- (6-CH 3 (CH} 2) 11) pyrophosphate, tetra- (1-CH ₃ (CH _{2) 12)} pyrophosphate, tetra- (2-CH ₃ (CH _{2) 12)} pyrophosphate, tetra- ( 3-CH ₃ (CH ₂ ) ₁₂ ) pyrophosphate, tetra- (4-CH ₃ (CH ₂ ) ₁₂ ) pyrophosphate, tetra- (5-CH ₃ (CH ₂ ) ₁₂ ) pyrophosphate, tetra- (6- CH ₃ (CH ₂ ) ₁₂ ) pyrophosphate, tetra-phenyl pyrophosphate, di-methyl- (di-ethyl) pyrophosphate, di-methyl- (di-phenyl) pyrophosphate and di-methyl- (di-4- Pentene) pyrophosphate.
[102] Examples of additional phosphorus containing compounds include those described in "Phosphorus Chemistry in Everyday Living" by A. Toy and E. Walsh (second edition, 1987, ACS, Washington, DC.). Contains: pyrophosphate, phosphorite, phosphorothioate, phosphorothioate, phosphonate, phosphorodithioate, bis-phosphorodithioate, phosphonodithioate, phosphoramidothioate And pyrophosphoramide Specific species include: tetra-propyl dithiono-pyrophosphate, tetra-ethyl dithiono-pyrophosphate, O-ethyl O- [2- (di-isopropyl amino) ethyl] methyl Phosphonite, O, O-dimethyl Op-nitrophenyl phosphorothioate, O, O-diethyl Op-nitrophenyl phosphothioate, O, O-dimethyl O- (4-nitro-m-tolyl) phosphate Porothioate, O-ethyl Op-nitrophenyl phenylphosphono Thioate, O, O-diethyl O- (3,5,6-trichloro-2-pyridyl) phosphorothioate, O, O-diethyl O- (2-isopropyl-6-methyl-4 -Pyridinyl) phosphorothioate, O, O-diethyl O- [4-methylsulfinyl) phenyl] phosphorothioate, O, O-dimethyl O- [3-methyl-4- (methyl thio) phenyl Phosphorothioate, O, O-dimethyl (2,2,2-trichloro-1-hydroxy-ethyl) phosphonate, 2,2-di-chlorovinyl di-methyl phosphate, 1,2-di -Bromo-2,2-di-chloroethyl dimethyl phosphate, 2-chloro-1- (2,3,4-trichloro-phenyl) vinyl dimethyl phosphate, O- (4-bromo-2-chloro-phenyl ) O-ethyl-S-propyl phosphoro-thioate, O-ethyl-O- [4- (methyl-thio) phenyl] S-propyl phosphorodithioate, O-ethyl S, S-di-propyl phosphate Porodithioate, diethyl mercaptosuccinate, S-ester with O, O-dimethyl phosphorodithioate, S-[(1,1-dimethyl-ethyl) thio] methyl] O, O- Ethyl phosphorodithioate, O, O-dimethyl S-phthalimido-methyl phosphorodithioate, O, O-dimethyl S-4-oxo-1,2,3-benzotriazine, 3- (4H ) -Ylmethyl phosphorodithioate, O, O, O ', O "'-tetraethyl S, S'-methylene bis-phosphorodithioate, S-[(6-chloro-2-oxo-3 -(2H) -benzoxazolyl) cetyl] O, O-di-ethyl phosphorodithioate, S-[(p-chlorophenyl-thio) methyl] O, O-diethyl phosphorodithioate, 1 , 4-p-dioxane-2,3-di-thiol S, S-bis (O, O-diethyl) phosphorodithioate, O-ethyl S-phenyl ethyl-phosphonodithioate, O, S-dimethyl phosphoramidothioate, O, S-dimethyl acetyl-phosphoramidothioate, 1-methylethyl 2-[[ethoxy [(1-methylethyl) amino] phosphinothio] oxy] benzo Ate, dimethyl-dichlorovinyl phosphate, O, O-diethyl S-ethyl-thiomethyl phosphorodithioate, O, O-dimethyl S- (methyl-carbamoylmethyl) foam Sporodithioate, Ethyl 3-methyl-4- (methylthio) phenyl (1-methylethyl) -phosphoamidate, O, O-dimethyl O- [2- (methcarbamoyl) -1-methyl-vinyl ] Phosphate and octamethylpyrophosphoramide.
[103] Specific examples of phosphinates are as follows: ethyl pentyl phosphinate, ethyl hexyl phosphinate, ethyl heptyl phosphinate, ethyl octyl phosphinate, ethyl decyl phosphinate, ethyl phenyl phosphinate, butyl pentyl phosphate Ffinate, butyl hexyl phosphinate, butyl heptyl phosphinate, pentyl dibutyl phosphinate, hexyl dibutyl phosphinate and heptyl dibutyl phosphinate.
[104] Examples of phosphinic acids are: pentyl phosphinic acid, hexyl phosphinic acid, heptyl phosphinic acid, octyl phosphinic acid, decyl phosphinic acid, phenyl phosphinic acid, dipentyl phosphinic acid, diheptyl phosphinic acid, didecyl phosphinic acid, diphenyl Phosphinic acid, phenyl hexyl phosphinic acid and pentyl decylphosphinic acid.
[105] Examples of phosphinoic acids are as follows: monopentyl phosphinoic acid, monohexyl phosphinoic acid, monoheptyl phosphinoic acid, monooctyl phosphinoic acid, monodecyl phosphinoic acid, monophenyl phosphinoic acid, dipropyl phosphino Acids, dipentyl phosphinoic acid, diheptyl phosphinoic acid, didecyl phosphinoic acid, diphenyl phosphinoic acid and propyl decyl phosphinoic acid.
[106] Examples of phosphonates are: hexyl pentyl phosphonate, heptyl pentyl phosphonate, octyl pentyl phosphonate, decyl pentyl phosphonate, phenyl pentyl phosphonate, dibutyl pentyl phosphonate, dihexyl phosphate Phonates, heptyl phosphonates, pentyl phosphonates, octyl phosphonates and phenyl phosphonates.
[107] Examples of phosphonic acids are as follows: pentyl phosphonic acid, hexyl phosphonic acid, heptyl phosphonic acid, octyl phosphonic acid, decyl phosphonic acid, phenyl phosphonic acid, methyl pentyl phosphonic acid, methyl phenyl phosphonic acid, pentyl phosphonic acid, octyl phosphonic acid , Phenyl phosphonic acid and pentyl octyl phosphonic acid.
[108] Examples of phosphonites are: ethyl pentyl phosphonite, ethyl hexyl phosphonite, ethyl heptyl phosphonite, ethyl octyl phosphonite, ethyl decyl phosphonite, ethyl phenyl phosphonite, butyl pentyl phospho Nitrate, butyl hexyl phosphonite, butyl heptyl phosphonite, diethyl pentyl phosphonite, diethyl hexyl phosphonite and diethyl heptyl phosphonite.
[109] Examples of phosphono acids are as follows: 1-pentyl phosphono acid, 2-pentyl phosphono acid, 3-pentyl phosphono acid, 1-hexyl phosphono acid, 2-hexyl phosphono acid, 3-hexyl phosphono Acids, 1-heptyl phosphono acid, 2-heptyl phosphono acid, 3-heptyl phosphono acid, 4-heptyl phosphono acid, octyl phosphono acid, decyl phosphono acid and phenyl phosphono acid.
[110] The constituent material of the porous support of the composite membrane is not critical to the present invention. Any porous support that provides physical strength to the identification layer can be used so long as the size of the pores is large enough to not delay the passage of the permeate and does not interfere with the bridging-over of the resulting identification layer. Typical pore sizes range from 10 to 1,000 nm. Typical support materials known in the art include cellulose esters, polysulfones, polyether sulfones, polyvinyl chlorides, chlorinated polyvinyl chlorides, polyvinylidene fluorides, polystyrenes, polycarbonates, polyimides, polyacrylonitriles and polyesters. Include. A particularly preferred class as support material is polysulfone. The preparation of such supports is described in US Pat. Nos. 3,926,798 and 4,039,440 and 4,277,344, which are incorporated herein by reference. The size of the microporous support is generally 25 to 125 μm, preferably 40 to 75 μm.
[111] Various membrane forms are commercially available and used herein. These include spherical annular, hollow fiber or planar sheet membranes. In view of the composition of the membrane, the identification layer often has a hygroscopic polymer in addition to the polyamide coated on the surface of the identification layer. These polymers are anionic, cationic, neutral and amphoteric, such as polymerizable surfactants, polyvinyl alcohols, polyethylene imines and polyacrylic acids.
[112] The membranes of the present invention can be applied to various post-treatments as described in US Pat. Nos. 4,765,897, 5,876,602 and 5,755,964, incorporated herein by reference. Such aftertreatment may further enhance membrane performance, such as, for example, increased flow rates and / or reduced salt permeability.
[113] For example, in US Pat. No. 5,876,602, the membrane stability against strong base exposure (while maintaining the flow rate and salt permeability) is determined by forming the membrane on the porous support in the form of a flat sheet or component and then hypochlorite at pH 10.5 or higher. It can be achieved by contact with a solution. The optimal exposure time depends on the temperature and the concentration of hypochlorite used. At room temperature, conditions to reach the desired target are generally found to be within 10 minutes to 5 hours, with concentrations of 200 to 10,000 ppm by weight hypochlorite, depending on the chlorine. Preferred concentrations of hypochlorite are 500 to 7,000 ppm and the preferred exposure time is 30 to 3 hours. In a preferred embodiment, the membrane is heat treated prior to exposure to the aforementioned chlorine treatment. The membrane is heated in water for 30 seconds to 24 hours at a temperature of 40 ° C to 100 ° C. The heat treatment further lowers salt permeability and removes impurities contained in the membrane that can interfere with the beneficial results of the chlorine treatment. Depending on the desired product, two treatment conditions are adjusted within the range to improve salt permeability and at the same time maintain or improve flow rates over a single treatment. The two treatment sequences performed are important because the heat treatment of the membranes performed simultaneously or continuously with the chlorine treatment does not provide the improved results obtained by first chlorination of the membranes and then heat treatment.
[114] Another example of applicable aftertreatment is described in US Pat. No. 5,755,964, which comprises contacting the identification layer with an amine consisting of the following groups: ammonia unsubstituted or substituted with one or more alkyl groups of 1 to 2 carbon atoms Wherein the alkyl group may be unsubstituted or substituted with one or more substituents selected from hydroxy phenyl or amino, butylamine, cyclohexylamine, 1,6-hexanediamine and mixtures thereof. Preferably substituted ammonia materials include dimethylamine, trimethylamine, ethylamine, triethanolamine, N, N-dimethyl ethanolamine, ethylenediamine and benzylamine. By contacting the amines described above with the identification layer, the flow rate was increased, and it was found that the rejection rate for the particular material changed. The degree of flow rate of the increased or enhanced membrane can be controlled by various specific amines, concentrations of amines, contact time between the identification layer and the amine, contact temperature, pH of the amine solution, or a combination thereof. As the flow rate increases, the selectivity of the membrane changes, ie monovalent ions, such as sodium, can pass through the membrane at high speed, while changing the selectivity of the membrane to reject polyvalent ions and organic compounds.
[115] The amines used to treat the polyamide identification layer can be performed in solution, as is, or in gas phase, as long as they can be contacted with the polyamide. The gas phase can typically be used for low molecular weight amines such as ammonia, methylamine and dimethylamine. The solvent can be any solvent in which the amine is dissolved, as long as the flow rate enhancement and membrane performance are not hindered by contact with the solvent. Typical solvents include water in which the support is not dissolved by the solvent, and organic compounds such as alcohols and hydrocarbons. In general, water is used when a solvent is desired because of its ease of operation and its usefulness.
[116] The range of flow rates of the membrane is enhanced when treated with the various amines of the present invention depending on the particular amine used. However, in most cases it applies in more than one direction. It is a trend to have additional functional groups on the amines which greatly increase the flow rate, for example alcohols and / or amino groups. Similarly, the concentration of amine and the contact time are correlated and affect the degree of flow rate enhancement. The minimum time required to contact the identification layer to increase the flow rate depends on the very wide range of amine concentrations. In general, high concentrations of amines require short contact times to increase flow rates. In most cases, the concentration of amine is about 5, preferably at least about 20, most preferably at least about 50 to about 100% by weight. The minimum contact time is at least about 15 seconds, preferably at least about 1 minute, more preferably at least about 30 minutes, when contacting at room temperature.
[117] In general, the longer the contact time or the higher the amine concentration, the higher the flow rate. After prolonging the contact time, the flow rate increases to the maximum and then no longer increases. At this point, the membrane can be used or kept in the amine. The time to reach maximum increase depends on the specific amine, amine concentration and contact temperature used, but can be ascertained by one skilled in the art without undue experimentation by using the general trend described above. For most amines and concentrations, the flow rate of the membrane can be maximized when the identification layer is in contact with the amine for about 5 days. If it is desired to minimize the contact time, the surface temperature of the polyamide identification layer can be increased. Although this application is common, it is particularly effective when low concentrations of amines are used which require long contact times. Although temperatures from 0 ° C. to 30 ° C. are most commonly used, increased temperatures can shorten the required contact time. The increased temperature should not be too high so as not to reduce the performance of the membrane, ie not greater than about 130 ° C. Typical temperatures which promote the flow rate effect of the membrane are at least about 30 ° C, preferably from about 60 ° C to about 130 ° C. These temperatures can be achieved by contacting the amine with the polyamide identification layer in a device such as an oven or dryer. Typical ovens or dryers that can be used include convection, infrared or pressurized air dryers.
[118] The pH of the amine solution in contact with the polyamide is not critical to the present invention. However, the pH should not be so low that the particular amine used is precipitated out of solution. In contrast, the pH should not be so high that the polyamide identification layer will degrade or lose performance. Preferably, about pH 7 to about 12 are useful in the method of the present invention, and certain amines may increase the degree of flow rate enhancement at high pH.
[119] The method used to contact the identification layer with the amine can be any method that allows the amine to bond with the polyamide for a sufficient time to increase the flow rate. For example, the polyamide may be partially or completely immersed or submerged in the amine or amine solution. The amine or amine solution can also be passed, sprayed or rolled through the identification layer. Where the amine is a gas, the aforementioned method may be useful, but the contact of the gaseous amine with the identification layer is effectively accomplished in a sealed container to minimize the amount of amine used.
[120] Improved flow rate and rejection properties are achieved by posttreatment of the membrane by contacting strong acids such as, for example, phosphoric acid, polyphosphoric acid, triphosphate, sulfuric acid, and the like. About 10 to 85 weight percent phosphoric acid is particularly suitable. As described in US Pat. No. 4,765,987, the membrane can be contacted with a mine by spraying an aqueous solution of acid on the membrane or immersing the membrane in an acid water bath. In certain embodiments, the acid solution may be heated. When treated with a mineral mine, the membrane may be further treated with rejection enhancers (eg, colloids, tannic acids, polyamidoamines, etc.) as described in US Pat. No. 4,765,897.
[121] The term as used herein has the following definition: "Rejection rate" is the proportion of a particular dissolved or dispersed material (ie, solute) that does not flow through the membrane using a solvent. The rejection rate is equal to 100 minus the percentage of dissolved or dispersed material permeating through the membrane, ie solute permeation ("salt permeation" if the dissolved material is a salt). "Flow Rate" is the flow rate per unit area when solvent, typically water, permeates through the membrane. A "reverse osmosis membrane" is a membrane with a rejection rate of about 95 to 100% for NaCl. A "nanofiltration membrane" is a membrane with a rejection rate of NaCl of about 0 to about 95% and a rejection rate of one or more divalent ions or organic compounds of about 20 to about 100% 5. "Polyamide" is a polymer in which amide linkages (-C (O) NH-) occur along the molecular chain. "Complexing agent", "amine" and "acrylic halide" 'mean a single species or a mixture of multiple species. For example, the term "amine" may mean a mixture of multifunctional amine monomers. The terms "% by weight", "% by weight" and "% by weight" mean 100 x (g / g of solvent 100 ml).
[122] The following examples are intended to aid the description of the invention and are not intended to limit the scope of the claimed claims. Unless otherwise indicated, composite membranes are prepared in the laboratory using porous polysulfone supports formed from 16.5% polysulfone solutions in DMF. The support is cut into rectangles (11 inches, 7 inches), clipped onto a wire frame (10 inches, 7.5 inches) and placed in 2.5% by weight meta phenylene diamine (MPD) solution for about 20 minutes. The support submerged in MPD is then placed on a paper towel and rolled with a rubber roller to remove excess solution from the front and back surfaces. The support is then placed on a plastic sheet and a silicone rubber gasket is placed around the edge. Cut the plastic sheet to the same size as the opening of the gasket. This is fixed to form a leak proof seal at the edge. Then 50 ml of isopar L solution of trimesolol chloride (TMC) (0.09 wt%) containing the complexing agent in a 1: 2 stoichiometric ratio (TMC: complexing agent) is poured from the top. The specific complexing agents used in each example are shown in the table below. The control sample does not contain any complexing agents. After reacting for 1 minute, the TMC solution is poured, the membrane is washed with hexane and dried for the time shown in the table below. The formed composite membrane is then placed in water and tested at a pressure of 130 psi using 2000 ppm of NaCl solution at pH 6.5-8. The membrane is tested under these test conditions for 30 minutes, then the permeability is collected and analyzed. The results are shown in the table below. Due to the variety of preparation and test conditions, separate control membranes are prepared and tested using batches of membranes each prepared as indicated in the table below.
[123] Example numberComplexing agentDrying time (seconds)Flow rate (gfd)Salt transmittance (%) 1 (control)None6011.70.79 2Tri-methyl phosphate6023.32.7 3Tri-ethyl phosphate6013.40.46 4Tri-butyl phosphate6020.30.88
[124] Example numberComplexing agentDrying time (seconds)Flow rate (gfd)Salt transmittance (%) 5 (control)None6012.11.2 6Dibutyl phosphite6014.40.62
[125] Example numberComplexing agentDrying time (seconds)Flow rate (gfd)Salt transmittance (%) 7 (control)None1014.70.7 8Bis (2-ethylhexyl) phosphite1023.71.06
[126] Example numberComplexing agentDrying time (seconds)Flow rate (gfd)Salt transmittance (%) 9 (control)None1013.70.69 10Triphenyl phosphine1022.112.6 11Triethyl phosphate1020.51.5
[127] Example numberComplexing agentDrying time (seconds)Flow rate (gfd)Salt transmittance (%) 12 (control)None1016.60.26 13Triphenyl phosphine1031.83.32 14Triphenyl phosphate1022.90.34
[128] Example numberComplexing agentDrying time (seconds)Flow rate (gfd)Salt transmittance (%) 15 (control)None1012.60.35 16Triphenyl phosphine1017.70.41 17Tributyl phosphate1016.20.53
[129] Example numberComplexing agentDrying time (seconds)Flow rate (gfd)Salt transmittance (%) 18 (control)None1012.00.38 19Di-tert-butyl diisopropyl phosphoramidite [(CH ₃ ) ₂ CH] ₂ NP [OC (CH ₃ ) ₃ ] ₂ 1016.00.45
[130] Example numberComplexing agentDrying time (seconds)Flow rate (gfd)Salt transmittance (%) 20 (control)None1013.80.38 21Dibutylbutyl phosphonate CH ₃ (CH ₂ ) ₃ P (O) [O (CH ₂ ) ₃ CH ₃ ] ₂ 1016.10.30 22Tri-octyl phosphine1017.50.39
[131] * TMC and tri-octyl phosphine are in a 4: 1 stoichiometric ratio.
[132] Example numberComplexing agentDrying time (seconds)Flow rate (gfd)Salt transmittance (%) 23 (control)None3011.90.49 24Ferrocene 50mM3014.70.39 25Ferrocene 100mM3016.50.37
[133] Example numberComplexing agentDrying time (seconds)Flow rate (gfd)Salt transmittance (%) 26 (control)None1014.20.341 27Triphenyl Bismuth 5mM1012.80.341
[134] Example numberComplexing agentDrying time (seconds)Flow rate (gfd)Salt transmittance (%) 28 (control)None1016.60.259 29Triphenyl Phosphine 2.5mM1031.83.32 30Triphenyl Phosphate 2.5mM1022.90.343 31Triphenyl Arsine 2.5mM1029.90.498 32Triphenyl Antimony 2.5mM1025.10.442
[135] Tables 10 and 11 show the differences in performance associated with the use of various triphenyl metal and nonmetal complexing agents. As shown in Table 10, when used in systems comprising TMC and Isopar L solutions, trioctyl bismuth is not a preferred complexing agent.
[136] Example numberComplexing agentDrying time (seconds)Flow rate (gfd)Salt transmittance (%) 33 (control)None1013.70.30 34Trioctyl Aluminum 3mM1040.972 35Tributyl Phosphate 5 mM1019.470.42
[137] Table 12 shows preferred complexing agents for using TMC and Isopar L solutions (Example 35) and complexing agents believed to include total energy values above the desired range of the present invention, as evidenced by unpredictable salt permeability. The difference in performance between Example 34) is shown.
[138] Example numberComplexing agentDrying time (seconds)Flow rate (gfd)Salt transmittance (%) 36 (control)None1019.00.45 37Fe (III) Tris TMH1016.720.326 38Fe (II) Bis Acac1022.80.65 39Fe (iii) Tris Acac1024.00.71
[139] Example numberComplexing agentDrying time (seconds)Flow rate (gfd)Salt transmittance (%) 40 (control)None1018.30.48 41Co (III) Tris Acac1019.50.96 42Cr (III) Tris Acac1022.00.50
[140] The term "Acac" refers to acetylacetonate (2,4 pentane-dione) and "TMH" refers to 2,2,6,6 tetramethyl-3,5 heptanedioonate. The tests for Examples 36-42 were completed using 2000 ppm NaCl at 150 psi. The TMC solution for Example 37 is prepared at a complexing agent concentration of 2.5 mM, whereas the TMC solution for Examples 38, 39, 41 and 42 is a saturated solution that does not contain a residual amount of undissolved portion. Thus, the solution used in Examples 38, 39, 41 and 42 is less than 2.5 mM.
[141] As shown in the table provided above, the addition of the complexing agent to the polyfunctional acyl halide solution can improve the flow rate and / or rejection rate (eg salt permeability) of the resulting membrane.

权利要求:
Claims (36)
[1" claim-type="Currently amended] A method for producing a composite membrane comprising interfacially polymerizing a polyfunctional amine and a polyfunctional acyl halide on a surface of a porous support to form a polyamide layer.
Prior to reacting the polyfunctional acyl halide with the polyfunctional amine, the complexing agent (wherein the complexing agent has a bonding center selected from group IIIA to VIB groups of the IUPAC periodic table and non-sulfur atoms selected from 3 to 6 cycles) and the polyfunctional acyl Contacting a halide.
[2" claim-type="Currently amended] The method of claim 1, wherein the contacting of the complexing agent with the polyfunctional acyl halide is carried out in a reverse osmosis fashion using pure water fed through the membrane at a flow rate of 24 gfd through the membrane with a permeation recovery of 0.5% to 25%. A method of producing a polyamide layer having a detectable amount of binding center of conserved complexing agent therein after operating at 25 ° C. for 24 hours.
[3" claim-type="Currently amended] The method of claim 2 wherein the polyamide layer has at least 25 μg per gram of polyamide where the polyamide layer is preserved.
[4" claim-type="Currently amended] The method of claim 1 wherein the total energy change resulting from the interaction of the polyfunctional acyl halide with the complexing agent is about 3.5-20 kcals / mole.
[5" claim-type="Currently amended] 5. The method of claim 4 wherein the solubility parameter of the complexing agent is 18-23 J ^1/2 cm ^-3/2 and the total energy change resulting from the interaction of the polyfunctional acyl halide with the complexing agent is 5.0-15.0 kcals / mole. .
[6" claim-type="Currently amended] The method of claim 1 wherein the solubility parameter of the complexing agent is from about 15 to about 26 J ^1/2 cm ^−3/2 .
[7" claim-type="Currently amended] The method of claim 1, wherein the complexing agent is a compound of formula 1.
Formula 1
α (L _x β) _y
In Formula 1 above,
α is the bond center,
L is a chemical bonding group, the same or different,
β is a solubilizing group and is the same or different and contains 1 to 12 carbon atoms,
x is an integer from 0 to 1,
y is an integer from 1 to 5.
[8" claim-type="Currently amended] The method of claim 1 wherein the bonding center of the complexing agent is a metal.
[9" claim-type="Currently amended] The method of claim 1 wherein the bonding center of the complexing agent is selected from silicon and selenium.
[10" claim-type="Currently amended] The method of claim 1 wherein the bonding center of the complexing agent is selected from one or more of Al, Si, P, As, Sb, Bi, Se, Te, Fe, Cr, Co, Ni, Cu, and Zn elements.
[11" claim-type="Currently amended] The polyfunctional amine of claim 1, wherein the polyfunctional amine is provided as an aqueous solution, wherein the polyfunctional acyl halide is a complexing agent, wherein the complexing agent is substantially soluble in the nonaqueous solution and has a solubility parameter of about 15 to about ²⁶ J ^1/2 cm ^{-3. / 2} ), wherein the solutions are continuously coated on the surface of the porous support.
[12" claim-type="Currently amended] The complexing agent of claim 1, wherein the complexing agent has a binding center of phosphorus, and the phosphate, phosphite, phosphine, phosphine oxide, phosphonate, diphosphonate, phosphinate, phosphinite, phosphonite, pyrophosphate, fatigue And at least one of the compound classes of phosphoramides, phosphoramides, phosphorothionates, phosphorodithionates and phosphoramido thionates.
[13" claim-type="Currently amended] The method of claim 1 wherein the complexing agent comprises a compound of formula (2).
Formula 2

In Formula 2 above,
Z is the same or different and X, OP- (X) ₂ , P (O) -X ₂ , (P (-X)) _m -PX ₂ , (OP (-X)) _m -OPX ₂ , (P (O) (-X)) _m -P (O) -X ₂ and (OP (O) (-X)) _m -OP (O) -X ₂ [where P is phosphorus and O is oxygen, m is an integer from 1 to 5, Y is O or an unbonded electron pair, X is the same or different, and R or R comprising one or more oxygen and / or alkyl bond (s), wherein R is the same or different Selected from H and a carbon-containing moiety).
[14" claim-type="Currently amended] The method of claim 13, wherein Z is selected from a C _1-8 aliphatic group.
[15" claim-type="Currently amended] The method of claim 13, wherein at least one R is selected from aromatic groups or heterocyclic groups.
[16" claim-type="Currently amended] The compound of claim 13, wherein Y is oxygen, Z is the same or different, and R and R comprising one or more oxygen bonds, wherein R is the same or different, H and C_1-12 Selected from the containing moiety).
[17" claim-type="Currently amended] The method of claim 16, wherein R is selected from a C _1-8 aliphatic group.
[18" claim-type="Currently amended] The method of claim 16, wherein at least one R is selected from aromatic groups and / or heterocyclic groups.
[19" claim-type="Currently amended] The method of claim 13, wherein Y is an unbonded electron pair and the phosphorus containing compound comprises a compound of Formula 4. 15.
Formula 4

In Formula 4 above,
Z is the same or different and is selected from R and R comprising one or more oxygen and / or alkyl bonds, wherein R is the same or different and is selected from H and C _1-12 containing moieties.
[20" claim-type="Currently amended] The method of claim 19, wherein R is selected from a C _1-8 aliphatic group.
[21" claim-type="Currently amended] The method of claim 19, wherein at least one R is selected from aromatic groups.
[22" claim-type="Currently amended] The method of claim 19, wherein at least one R is selected from a heterocyclic group.
[23" claim-type="Currently amended] The method of claim 16, wherein the phosphorus containing compound comprises a compound of formula 5. 17.
Formula 5

[24" claim-type="Currently amended] The method of claim 23, wherein R is selected from a C _1-8 aliphatic group.
[25" claim-type="Currently amended] The method of claim 23, wherein at least one R is selected from aromatic and / or heterocyclic groups.
[26" claim-type="Currently amended] The porous support is coated with an aqueous solution containing a polyfunctional amine and then coated with an organic solution containing the polyfunctional acyl halide to contact and react the polyfunctional amine and the polyfunctional acyl halide with each other to form a polyamide layer on the porous support. As a method of manufacturing a composite membrane comprising the step,
Prior to reacting the polyfunctional acyl halides with the polyfunctional amine, the complexing agent, wherein the complexing agent has a solubility parameter of about 15 to about 26 J ^1/2 cm ^-3/2 , and groups IIIA to VIB of the conventional IUPAC periodic table and Contacting the polyfunctional acyl halide with a center of bonding comprising at least one atom selected from non-sulfur atoms selected from 3 to 6 cycles.
[27" claim-type="Currently amended] 27. The method of claim 26, wherein the bonding center of the complexing agent is selected from one or more of Al, Si, P, As, Sb, Se, Te, Fe, Cr, Co, Ni, Cu, Zn and Pb elements.
[28" claim-type="Currently amended] A polyamide layer immobilized on the porous support, wherein the polyamide layer comprises a non-sulfur element selected from Group IIIa to VIB elements and the 3 to 6 periodic elements of the conventional IUPAC periodic table, the elements having a permeability recovery of 0.5 And remains detectably inside the polyamide after 24 hours of operation at 25 ° C. in a reverse osmosis method using an integer supplied at a flow rate of 24 gfd through a membrane of% to 25%.
[29" claim-type="Currently amended] 29. The membrane of claim 28 which contains at least 25 μg element per gram of polyamide.
[30" claim-type="Currently amended] The membrane of claim 29, containing at least 50 μg element per gram of polyamide.
[31" claim-type="Currently amended] 33. The membrane of claim 30 containing at least 200 μg element per gram of polyamide.
[32" claim-type="Currently amended] 29. The membrane of claim 28 wherein the element is a metal.
[33" claim-type="Currently amended] 29. The membrane of claim 28 wherein the element is phosphorus.
[34" claim-type="Currently amended] 29. The membrane of claim 28 wherein the element is selected from silicon and selenium.
[35" claim-type="Currently amended] The membrane of claim 28, wherein the element is selected from one or more of Al, Si, As, Sb, Se, Te Fe, Cr, Co, Ni, Cu, and Zn elements.
[36" claim-type="Currently amended] The complexing agent of claim 28, wherein the complexing agent has a binding center of phosphorus, and the phosphate, phosphite, phosphine, phosphine oxide, phosphonate, diphosphonate, phosphinate, phosphinite, phosphonite, pyrophosphate, fatigue And at least one of the class of compounds of phosphoramide, phosphoramide, phosphorothionate, phosphorodithionate and phosphoramido thionate.

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同族专利:

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公开号 | 公开日

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IL152286D0|2003-05-29|

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ES2328449T3|2009-11-13|

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US20020113008A1|2002-08-22|

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CN1210093C|2005-07-13|

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JP2003531219A|2003-10-21|

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DE60139615D1|2009-10-01|

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TWI243707B|2005-11-21|

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US20030116498A1|2003-06-26|

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US6337018B1|2002-01-08|

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US20010050252A1|2001-12-13|

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DK1276551T3|2009-11-16|

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CN1441693A|2003-09-10|

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AU5524601A|2001-10-30|

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CA2403301C|2009-08-25|

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US6878278B2|2005-04-12|

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WO2001078882A2|2001-10-25|

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EP1276551A2|2003-01-22|

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US6723241B2|2004-04-20|

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IL152286A|2006-10-05|

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JP4932120B2|2012-05-16|

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CA2403301A1|2001-10-25|

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US6562266B2|2003-05-13|

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AU2001255246B2|2005-02-10|

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WO2001078882A3|2002-02-28|

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KR100839805B1|2008-06-19|

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EP1276551B1|2009-08-19|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2000-04-17|Priority to US09/550,527

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2000-04-17|Priority to US09/550,527

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2001-04-09|Application filed by 다우 글로벌 테크놀로지스 인크.

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2001-04-09|Priority to PCT/US2001/011265

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2003-01-06|Publication of KR20030001430A

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2008-06-19|Application granted

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2008-06-19|Publication of KR100839805B1

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2013-03-29|First worldwide family litigation filed

优先权:

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申请号 | 申请日 | 专利标题

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US09/550,527|US6337018B1|2000-04-17|2000-04-17|Composite membrane and method for making the same|

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US09/550,527|2000-04-17|

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PCT/US2001/011265|WO2001078882A2|2000-04-17|2001-04-09|Composite membrane and method for making the same|