WO2019203208A1 - Dérivé de polyglycérine - Google Patents

Dérivé de polyglycérine Download PDF

Info

Publication number
WO2019203208A1
WO2019203208A1 PCT/JP2019/016243 JP2019016243W WO2019203208A1 WO 2019203208 A1 WO2019203208 A1 WO 2019203208A1 JP 2019016243 W JP2019016243 W JP 2019016243W WO 2019203208 A1 WO2019203208 A1 WO 2019203208A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
carbon atoms
glycerin
water
draw
Prior art date
Application number
PCT/JP2019/016243
Other languages
English (en)
Japanese (ja)
Inventor
秀人 松山
智輝 高橋
一郎 高瀬
豊三 浜田
陽子 橋爪
Original Assignee
株式会社ダイセル
国立大学法人神戸大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社ダイセル, 国立大学法人神戸大学 filed Critical 株式会社ダイセル
Publication of WO2019203208A1 publication Critical patent/WO2019203208A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/40—Succinic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Definitions

  • the present invention relates to a polyglycerin derivative useful when used as a draw solute in a membrane separation method using a forward osmosis membrane.
  • the forward osmosis membrane separation method is a membrane separation method that utilizes the phenomenon that water on the low osmotic pressure side moves toward a solution with a high osmotic pressure. Compared with the reverse osmosis membrane separation method, the energy consumption in membrane separation is This is advantageous in that it is reduced. In the forward osmosis membrane separation method, it is essential to use a draw solution containing a draw solute, and selection of the draw solute is important.
  • JP 2012-170954 A describes a forward osmosis inducer containing nitrogen atoms, a forward osmosis water treatment apparatus using the same, and a forward osmosis water treatment method represented by general formula 1. .
  • Japanese Patent Application Laid-Open No. 2015-47541 includes a temperature-responsive polymer that does not contain a nitrogen atom as a draw solute, and the temperature-responsive polymer is a polyvinyl ether polymer, a polyvinyl acetate polymer, (meth) acrylic. Those selected from acid-based polymers are described.
  • JP-A-2015-54292 discloses a nonionic surfactant having an HLB value of 10 or more, a nonionic surfactant having a lower HLB value than the surfactant, a fatty acid or an alcohol, or a mixture thereof. And using an attractant solution in which a temperature sensitive mixture having an average HLB value of 10 to 16 is dissolved in water.
  • the surfactant having an HLB value of 10 or more include polyglycerin monolaurate and polyoxyethylene sorbitan monolaurate, and the nonionic surfactant having an HLB value lower than that of the surfactant is sorbitan monocaprylate. Examples thereof include glycerin monocaprylate.
  • Japanese Patent Application Laid-Open No. 2017-170403 is represented by a polyglycerol having a specific molecular weight and a specific molecular weight as a draw solute, and a general formula (I) or (II). The use of polyglycerin derivatives is described.
  • An object of the present invention is to provide a polyglycerin derivative that is useful when used as a draw solute in a membrane separation method using a forward osmosis membrane.
  • the present invention relates to the following general formula (I):
  • GL is a glycerin residue
  • X is a C 1-10 alkylene group having a carbonyl bond (—CO—) as a linking group on the GL side
  • AO is a C 1-10 alkyleneoxy group
  • n Is the number of moles of AO added and represents 0 or 1.
  • R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a 3 to 10-membered cycloalkyl group, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and an acyl having 1 to 11 carbon atoms.
  • the polyglycerol derivative which has a repeating unit represented by this.
  • the present invention also relates to a draw solute containing the polyglycerin derivative.
  • the present invention is also a method for membrane separation using a forward osmosis membrane, A permeation step of bringing the water to be treated into contact with the draw solution containing the draw solute through the forward osmosis membrane, and moving the water contained in the water to be treated to the draw solution side; Including a separation step of separating water and the draw solute contained in the draw solution,
  • the present invention relates to a method for membrane separation using a forward osmosis membrane.
  • the polyglycerin derivative of the present invention When the polyglycerin derivative of the present invention is used as a draw solute in a membrane separation method using a forward osmosis membrane, the osmotic pressure of the draw solution containing the draw solute is high, and is appropriate for each concentration of the draw solution. Since it has a lower critical solution temperature (LCST), it is possible to reduce energy required to separate water from the water to be treated.
  • LCST critical solution temperature
  • the polyglycerol derivative of the present invention has the following general formula (I):
  • GL is a glycerin residue
  • X is a C 1-10 alkylene group having a carbonyl bond (—CO—) as a linking group on the GL side
  • AO is a C 1-10 alkyleneoxy group
  • n Is the number of moles of AO added and represents 0 or 1.
  • R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a 3 to 10-membered cycloalkyl group, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and an acyl having 1 to 11 carbon atoms.
  • the polyglycerol derivative which has a repeating unit represented by this.
  • GL is a glycerin residue and has any structure represented by the following formulas (1) and (2).
  • X is an alkylene group having 1 to 10 carbon atoms having a carbonyl bond (—CO—) as a linking group on the GL side, and the alkylene group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, 2 to 4 are more preferable.
  • the carbon number of the alkylene group is not counted in the carbon number of the alkylene group.
  • the alkylene group is preferably an ethylene group or a propylene group, and more preferably an ethylene group.
  • AO is an alkyleneoxy group having 1 to 10 carbon atoms, and the alkyleneoxy group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
  • the alkyleneoxy group is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group.
  • n is the number of added moles of AO and represents a number of 0 or 1. n is preferably 1.
  • R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a 3 to 10-membered cycloalkyl group, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and an acyl having 1 to 11 carbon atoms.
  • One or more selected from a group preferably one or more selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms, more preferably a hydrogen atom and carbon
  • R is an alkyl group having 1 to 10 carbon atoms
  • the alkyl group may be linear or branched, and the carbon number is preferably 1 to 8, more preferably 1 to 6, and more preferably 2 to 4 Is more preferable.
  • the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, iso-pentyl group, 3-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, sec-hexyl group, iso-hexyl group, 3-hexyl group, tert-hexyl group, neohexyl group, n-heptyl group , N-octyl group, n-non
  • the cycloalkyl group is preferably a 3- to 8-membered, more preferably 4- to 6-membered, still more preferably a 5- to 6-membered cycloalkyl group.
  • the cycloalkyl group include one or more groups selected from a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • R is an aryl group having 6 to 10 carbon atoms
  • the aryl group is one or more selected from a phenyl group, a naphthyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, and a xylyl group. Is mentioned.
  • R is an aralkyl group having 7 to 12 carbon atoms
  • examples of the aralkyl group include one or more selected from a benzyl group, a phenethyl group, and a naphthylmethyl group.
  • R is an acyl group having 1 to 11 carbon atoms
  • the acyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
  • the carbon number of the acyl group does not include carbon of the carbonyl group.
  • the acyl group include one or more selected from a methanoyl group, an ethanoyl group, a propanoyl group, a propenoyl group, a benzoyl group, an o-methylbenzoyl group, an m-methylbenzoyl group, and a p-methylbenzoyl group.
  • the number average molecular weight (Mn) of the polyglycerol derivative of the present invention is preferably 200 to 20,000, more preferably 300 to 10,000, and further preferably 500 to 5,000.
  • the number average molecular weight (Mn) of the polyglycerol derivative is measured by gel permeation chromatography (GPC). Specifically, it refers to a molecular weight in terms of polystyrene measured using chloroform, dimethylformamide, tetrahydrofuran, acetone, or a combination of these solvents as an eluent, preferably using tetrahydrofuran. More specifically, it can be measured by the method described in the examples.
  • the polyglycerol derivative of the present invention preferably has 1 to 100, more preferably 3 to 40, and still more preferably 3 to 10 repeating units represented by the general formula (I). .
  • the addition molar ratio of X and (AO) n —R to 1 mol of glycerol residue (GL) is GL:
  • X: (AO) n —R is: , Preferably 1: 0.1 to 1.7: 0.1 to 1.7, more preferably 1: 0.2 to 1.5: 0.1 to 1.5, and even more preferably 1: 0.5. To 1.5: 0.4 to 0.8, and more preferably 1: 0.6 to 0.95: 0.4 to 0.6.
  • the polyglycerin derivative of the present invention may have a monomer other than the repeating unit represented by the general formula (I).
  • the monomer other than the repeating unit represented by the general formula (I) is represented by the repeating unit of the glycerin monomer represented by the above formulas (1) and (2) and the following general formula (II). Repeat units are mentioned.
  • GL represents a glycerin residue
  • X represents an alkylene group having 1 to 10 carbon atoms having a carbonyl bond (—CO—) as a linking group on the GL side.
  • GL and X are the same as those described for the repeating unit represented by the general formula (I).
  • the repeating unit of the glycerol monomer shown by the said Formula (1) and (2) and the repeating unit represented by the following general formula (II) are the manufacturing processes of the repeating unit represented by the said general formula (I). It is obtained as a by-product.
  • the content of the repeating unit represented by the general formula (I) is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and still more preferably 90 to 100% by mass. Or 100% by mass.
  • the polyglycerin derivative of the present invention has, for example, a polyglycerin (PGL) having a number average molecular weight (Mn) of 120 to 12,000 and a primary hydroxyl group of 50% or more of all the hydroxyl groups.
  • PGL polyglycerin
  • Mn number average molecular weight
  • X followed by AO and R.
  • AO AO
  • R two or more of them may be used in combination.
  • the polyglycerin (PGL) can be synthesized using a polymerizable glycerin equivalent such as glycidol as a raw material, and has a highly branched structure in which 50% or more of the hydroxyl groups of the whole polyglycerin are primary hydroxyl groups. Is preferred.
  • the number average molecular weight (Mn) of the polyglycerol is preferably 120 to 12,000, more preferably 120 to 3,000, and still more preferably 200 to 1,000.
  • the number average molecular weight of the said polyglycerol is measured by said GPC.
  • the degree of polymerization of the polyglycerol is preferably 1 to 100, more preferably 3 to 40, and still more preferably 3 to 10.
  • hyperbranched poly (6) glycerin (trade name “PGL 06”, manufactured by Daicel Corporation), hyperbranched poly (20) glycerin (trade name “PGL20P”, Daicel Corporation) ), Highly branched poly (40) glycerin (trade name “PGLXP”, manufactured by Daicel Corporation) and the like can be suitably used (the number in parentheses is the polymerization degree of polyglycerin).
  • Examples of the method of introducing X of the general formula (I) into the polyglycerin and subsequently introducing AO and R include, for example, X is —C ( ⁇ O) CH 2 CH 2 —, AO is an ethyleneoxy group, When R is a -butyl group, there can be mentioned a method in which polyglycerin is subjected to a condensation reaction of succinic anhydride followed by a condensation reaction of 2-butoxyethanol.
  • the reaction for introducing X of the general formula (I) into polyglycerin is performed in the presence or absence of a solvent.
  • the solvent is not particularly limited as long as it is inert under the reaction conditions. Examples thereof include organic acids such as acetic acid, propionic acid and trifluoroacetic acid; nitriles such as acetonitrile, propionitrile and benzonitrile; formamide, acetamide, N , N-dimethylformamide (DMF), amides such as dimethylacetamide; Aliphatic hydrocarbons such as hexane, heptane, octane, cyclododecane; Aromatic hydrocarbons such as benzene, toluene, xylene; Chloroform, dichloromethane, dichloroethane, Halogenated hydrocarbons such as carbon chloride, chlorobenzene and trifluoromethylbenzene; nitro compounds such as nitrobenzene, nitrome
  • the subsequent reaction for introducing AO and R of the general formula (I) is also performed in the presence or absence of a solvent.
  • a solvent Any solvent may be used as long as it is inert under the reaction conditions, and examples thereof include water, dimethyl sulfoxide (DMSO), DMF, and other solvents exemplified above.
  • a base an amine such as triethylamine, a nitrogen-containing aromatic heterocyclic compound such as pyridine
  • an acid a condensing agent, or the like may be used as necessary depending on the type of reaction.
  • the reaction temperature can be appropriately selected depending on the type of reaction, the type of compound used, the type of solvent, etc., and is not particularly limited. For example, it is about 0 to 250 ° C., preferably about 25 to 150 ° C., more preferably about 50 to 150 ° C. Depending on the type of reaction, the reaction may proceed smoothly near room temperature.
  • the reaction may be carried out under an inert gas atmosphere such as nitrogen or argon, or under an air atmosphere or an oxygen atmosphere.
  • the draw solute of the draw solution used in the method for membrane separation using the forward osmosis membrane of the present invention contains a polyglycerin derivative having a repeating unit represented by the above general formula (I).
  • the content of the polyglycerol derivative having the repeating unit represented by the general formula (I) is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, More preferably, it is 30 to 100% by mass, still more preferably 60 to 100% by mass, and may be 100% by mass.
  • the method of membrane separation using the forward osmosis membrane of the present invention is a method of using the one containing the polyglycerol derivative of the present invention as a draw solute.
  • the forward osmosis membrane (semipermeable membrane) used in the present invention has a dense layer on one side and a support layer (non-dense layer) having a sparser structure than the dense layer on the opposite side to the dense layer. It is what you are doing.
  • the material of the forward osmosis membrane (semi-permeable membrane) is not particularly limited, and examples thereof include cellulose acetate-based, polyamide-based, polyethyleneimine-based, polysulfone-based, and polybenzimidazole-based materials. Cellulosic materials (cellulose triacetate materials) are preferred.
  • a forward osmosis membrane made of cellulose acetate is preferable because a high water permeation rate can be obtained by the interaction between the support layer and the above-described draw solution containing the draw solute.
  • the form of the forward osmosis membrane is not particularly limited, and a flat membrane, a tubular membrane, a hollow fiber membrane and the like can be used.
  • the draw solution containing the draw solute containing the polyglycerin derivative of the present invention exhibits high osmotic pressure when the water to be treated is seawater, the water contained in the water to be treated is easily moved to the draw solution side. be able to.
  • the polyglycerin derivative of the present invention is a temperature-sensitive polymer having a lower critical solution temperature (LCST) of 100 ° C. or lower, and those can be separated into two phases by heating to a temperature lower than the lower critical solution temperature (LCST). it can.
  • LCST lower critical solution temperature
  • the draw solute containing the polyglycerol derivative of the present invention is used and seawater is used as the water to be treated, it is preferably heated to a temperature 5 to 25 ° C. higher than the seawater temperature.
  • the water separated from the draw solution can be further purified by various methods as necessary and used as industrial water, drinking water, and the like.
  • the draw solute separated from the draw solution can be recovered and reused.
  • the succinylation rate and oligoethylene glycolation rate were calculated by the following methods.
  • the molar ratio of the succinyl group to the glycerin skeleton was calculated from the area ratio of the signal derived from the 1 H-NMR glycerin skeleton and the signal derived from the succinyl group of the polyglycerin derivative obtained by condensation reaction of the linker moiety, was used to obtain the succinylation rate.
  • Example 1 (1) Synthesis of succinylated poly (6) glycerin In a 2000 ml four-necked flask equipped with a Dimroth condenser and thermometer, 460.27 g of succinic anhydride and 560 ml of pyridine were added under a nitrogen atmosphere, and the mixture was stirred at 60 ° C. Heated. A solution prepared by dissolving 118.93 g of hyperbranched poly (6) glycerin (trade name “PGL 06”, manufactured by Daicel Corporation) in 660 ml of pyridine was added over 10 minutes. After completion of the addition, the mixture was reacted at 60 ° C.
  • PGL 06 hyperbranched poly (6) glycerin
  • BMEG-Suc-HPG06 was placed in two batch-type flat membrane test cells (C40-B, manufactured by Nitto Denko Corporation) equipped with a regenerated cellulose ultrafiltration membrane (PLAC07610, manufactured by Merck Millipore). Then, 203 g of the crude product was charged by half, and pure water was supplied using a pressure pump so that the internal pressure of the cell became 2.0 to 3.5 MPa. As a result of continuing to supply pure water sufficiently until the filtrate contained no solute, the amount of pure water used was 13 L. Finally, the aqueous solution remaining in the test cell was collected and concentrated with an evaporator. As a result, 16 g of a purified product of BMEG-Suc-HPG06 as a target product was obtained.
  • C40-B manufactured by Nitto Denko Corporation
  • PLAC07610 regenerated cellulose ultrafiltration membrane
  • BMEG-Suc-HPG06 has a repeating unit represented by the general formula (I) wherein X is an ethylene group having a carbonyl bond on the GL side, AO is an ethyleneoxy group, n is 1, and R is an n-butyl group It is a polyglycerin derivative.
  • Mn number average molecular weight in terms of polystyrene was 1,995.
  • succinylation rate and the carboxylic acid terminal modification rate were calculated based on the integration ratio of the peak derived from the polymer skeleton, and the succinylation rate was 90% and the carboxylic acid terminal modification rate was 45%.
  • Example 2 Synthesis of isobutyl monoethylene glycol-terminated succinylated poly (6) glycerin (iBMEG-Suc-HPG06)
  • the raw material was 51 g of succinylated poly (6) glycerin obtained by the synthesis of Example 1 (1), 90 ml of acetonitrile, 353 ml of triethylamine Synthesis and purification were carried out in the same manner as in Example 1 (2) except that 168 ml of ethylene glycol isobutyl ether (iBMEG), 9.3 g of DMAP, and 251 g of EDCI were changed to obtain 16 g of brown transparent iBMEG-Suc-HPG06.
  • iBMEG ethylene glycol isobutyl ether
  • iBMEG-Suc-HPG06 has a repeating unit represented by the general formula (I) wherein X is an ethylene group having a carbonyl bond on the GL side, AO is an ethyleneoxy group, n is 1, and R is an iso-butyl group It is a polyglycerin derivative.
  • Mn number average molecular weight in terms of polystyrene was 2,161.
  • the succinylation rate and the carboxylic acid terminal modification rate were calculated based on the integral ratio of the peak derived from the polymer backbone, and the succinylation rate was 90% and the carboxylic acid terminal modification rate was 48%.
  • Example 1 (2) synthesis and purification were performed in the same manner as in Example 1 (2), except that the raw material butoxyethanol was changed to the substances shown in Table 1, and each polyglycerin derivative was obtained.
  • Each of the obtained polyglycerin derivatives is a compound in which X in the general formula (I) is an ethylene group having a carbonyl bond on the GL side, AO is an ethyleneoxy group, n is 1, and R is a substituent described in Table 1 It is.
  • Table 1 shows the number average molecular weight (Mn), the succinylation rate, and the carboxylic acid terminal modification rate of each obtained polyglycerin derivative.
  • EDEG-Suc-HPG06 is a polyglycerin having a repeating unit represented by the general formula (I) wherein X is an ethylene group having a carbonyl bond on the GL side, AO is an ethyleneoxy group, n is 2, and R is an ethyl group Is a derivative.
  • the number average molecular weight (Mn) in terms of polystyrene was 1,697.
  • the succinylation rate was calculated based on the integration ratio of peaks derived from the polymer skeleton, and it was 96%.
  • Comparative Example 2 (1) Synthesis of succinylated poly (40) glycerin A highly branched poly (40) glycerin (trade name “PGLXP”, Co., Ltd.) in a 500 ml four-necked flask equipped with a Dimroth cooler and thermometer. 14 g of Daicel) was dissolved in 54 ml of pyridine. A solution prepared by dissolving succinic anhydride 59 g in 154 ml of pyridine was added to this solution and reacted at 60 ° C. for 7 hours with stirring. Thereafter, the reaction solution was allowed to stand overnight in a refrigerator and then filtered, and the filtrate was concentrated under reduced pressure.
  • PGLXP highly branched poly (40) glycerin
  • the supernatant was extracted, and the precipitate was concentrated under reduced pressure to dissolve the brown oil obtained by adding 30 ml of water and 30 ml of methanol. This solution was added to 150 ml of diethyl ether while stirring, and then allowed to stand at room temperature for 3 hours to precipitate the desired product again. The supernatant was extracted, and the precipitate was concentrated under reduced pressure to obtain a brown oil. Further, this brown oil was purified by a dialysis tube (MWCO2000), and the internal solution was concentrated under reduced pressure to obtain 9 g of MTEG-Suc-HPG40.
  • MWCO2000 dialysis tube
  • MTEG-Suc-HPG40 is a polyglycerin having a repeating unit represented by the general formula (I) wherein X is an ethylene group having a carbonyl bond on the GL side, AO is an ethyleneoxy group, n is 3, and R is a methyl group Is a derivative.
  • the number average molecular weight (Mn) in terms of polystyrene of the polyglycerin derivatives of Examples 1 to 9 and Comparative Examples 1 and 2 was measured by gel permeation chromatography (GPC) under the following conditions.
  • Solvent THF (manufactured by Kanto Chemical Co., Inc., HPLC grade) Flow rate: 0.6 ml / min
  • FIG. 1 shows the relationship between the concentration of the draw solution using the polyglycerin derivative obtained in Example 1 and Comparative Examples 1 and 2 (in FIG. 1, “wt%” means mass%) and osmotic pressure It was.
  • the measurement was performed 3 to 5 times, and the average value was used as the water content.
  • the concentration of the polyglycerin derivative was calculated from the obtained water content.
  • the aqueous polyglycerin derivative solution obtained in Example 1 was phase-separated at a temperature of 50 ° C. or higher, and the concentration of the lower polyglycerin derivative was 15.1% (50 ° C.).
  • the aqueous polyglycerin derivative solution obtained in Example 2 was phase-separated at a temperature of 20 ° C. or higher, and the concentration of the polyglycerin derivative in the lower phase was 25.0% (20 ° C.).
  • the aqueous polyglycerin derivative solution obtained in Comparative Example 2 was phase-separated at a temperature of 60 ° C. or higher, and the concentration of the lower polyglycerin derivative was 14.8% (60 ° C.).
  • the polyglycerol derivative obtained in Comparative Example 1 was also measured, but no phase separation was observed in the range of
  • the draw solution using the polyglycerin derivative of the present invention is an aqueous solution having an osmotic pressure higher than 1150 mmol / kg which is the osmotic pressure of seawater even in a relatively low concentration region (40 to 50% by mass). And can be used as a draw solution in the forward osmosis membrane separation method because it can be phase separated from water by heating to about 20 ° C. to 80 ° C.
  • the draw solute of the present invention and the forward osmosis membrane separation method using the same can be used, for example, in a seawater desalination method.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Polyethers (AREA)

Abstract

L'invention concerne un dérivé de polyglycérine qui peut être utilisé de manière utile en tant que soluté d'extraction dans un procédé de séparation par membrane à l'aide d'une membrane d'osmose directe. L'invention concerne un dérivé de polyglycérine ayant une unité de répétition représentée par la formule générale (I) [dans laquelle GL représente un résidu de glycérine ; X représente un groupe alkylène ayant une liaison carbonyle (-CO-) en tant que groupe de liaison sur le côté GL et ayant de 1 à 10 atomes de carbone ; AO représente un groupe alkylèneoxy ayant de 1 à 10 atomes de carbone ; n est le nombre de moles de AO ajoutées et représente une valeur numérique de 0 ou 1 ; et R représente au moins un élément choisi parmi un atome d'hydrogène, un groupe alkyle ayant de 1 à 10 atomes de carbone, un groupe cycloalkyle de 3 à 10 chaînons, un groupe aryle ayant de 6 à 10 atomes de carbone, un groupe aralkyle ayant de 7 à 12 atomes de carbone et un groupe acyle ayant de 1 à 11 atomes de carbone].
PCT/JP2019/016243 2018-04-16 2019-04-16 Dérivé de polyglycérine WO2019203208A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018078500A JP2019182812A (ja) 2018-04-16 2018-04-16 ポリグリセリン誘導体
JP2018-078500 2018-04-16

Publications (1)

Publication Number Publication Date
WO2019203208A1 true WO2019203208A1 (fr) 2019-10-24

Family

ID=68240189

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/016243 WO2019203208A1 (fr) 2018-04-16 2019-04-16 Dérivé de polyglycérine

Country Status (2)

Country Link
JP (1) JP2019182812A (fr)
WO (1) WO2019203208A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007091580A1 (fr) * 2006-02-07 2007-08-16 Nippon Biologicals, Inc. Nouveau transporteur de vaccin
JP2010100818A (ja) * 2008-04-17 2010-05-06 Daicel Chem Ind Ltd 温度感受性高分子化合物及び温度感受性薬剤放出システム
JP2010260986A (ja) * 2009-05-11 2010-11-18 Daicel Chem Ind Ltd ポリグリシドール誘導体、及びこれを含む複合薬物担体
JP2012170954A (ja) * 2011-02-18 2012-09-10 Samsung Electronics Co Ltd 正浸透用誘導溶液、これを用いた正浸透水処理装置、および正浸透水処理方法
KR20150012824A (ko) * 2013-07-26 2015-02-04 한국원자력연구원 유도용질용 자성 나노입자 및 그 제조방법
JP2015047541A (ja) * 2013-08-30 2015-03-16 東洋紡株式会社 正浸透水処理方法および正浸透水処理装置およびドロー溶液
JP2015054292A (ja) * 2013-09-12 2015-03-23 Ｊｆｅエンジニアリング株式会社 半透膜による水処理方法
JP2015054293A (ja) * 2013-09-12 2015-03-23 Ｊｆｅエンジニアリング株式会社 半透膜による水処理方法
JP2017170403A (ja) * 2016-03-25 2017-09-28 国立大学法人神戸大学 正浸透膜を使用して膜分離する方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007091580A1 (fr) * 2006-02-07 2007-08-16 Nippon Biologicals, Inc. Nouveau transporteur de vaccin
JP2010100818A (ja) * 2008-04-17 2010-05-06 Daicel Chem Ind Ltd 温度感受性高分子化合物及び温度感受性薬剤放出システム
JP2010260986A (ja) * 2009-05-11 2010-11-18 Daicel Chem Ind Ltd ポリグリシドール誘導体、及びこれを含む複合薬物担体
JP2012170954A (ja) * 2011-02-18 2012-09-10 Samsung Electronics Co Ltd 正浸透用誘導溶液、これを用いた正浸透水処理装置、および正浸透水処理方法
KR20150012824A (ko) * 2013-07-26 2015-02-04 한국원자력연구원 유도용질용 자성 나노입자 및 그 제조방법
JP2015047541A (ja) * 2013-08-30 2015-03-16 東洋紡株式会社 正浸透水処理方法および正浸透水処理装置およびドロー溶液
JP2015054292A (ja) * 2013-09-12 2015-03-23 Ｊｆｅエンジニアリング株式会社 半透膜による水処理方法
JP2015054293A (ja) * 2013-09-12 2015-03-23 Ｊｆｅエンジニアリング株式会社 半透膜による水処理方法
JP2017170403A (ja) * 2016-03-25 2017-09-28 国立大学法人神戸大学 正浸透膜を使用して膜分離する方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
INADA, ASUKA ET AL.: "Development of LCST-type phase transition polymer having glycerol skeleton, and its performance evaluation as forward osmosis draw solute", LECTURE PROGRAMS OF THE 83RD RESEARCH PRESENTATION OF THE SOCIETY OF CHEMICAL ENGINEERS, 13 March 2018 (2018-03-13), Japan *
KOJIMA C., ET AL.: "Temperature-sensitive hyperbranched poly(glycidol)s with oligo(ethylene glycol) monoethers", JOURNAL OF POLYMER SCIENCE : PART A: POLYMER CHEMISTRY, vol. 48, 2010, pages 4047 - 4054, XP055645984 *
SAKAGUCHI N., ET AL.: "The correlation between fusion capability and transfection activity in hybridcomplexes of lipoplexes and pH-sensitive liposomes", BIOMATERIALS, vol. 29, 2008, pages 4029 - 4036, XP023611048 *

Also Published As

Publication number Publication date
JP2019182812A (ja) 2019-10-24

Similar Documents

Publication Publication Date Title
CN110183402B (zh) 纳米过滤膜和使用方法
JP6460366B2 (ja) アミノ基を一つ有するポリエチレングリコールの精製方法
WO2019203208A1 (fr) Dérivé de polyglycérine
Pithan et al. Synthesis of highly fluorinated copolyimide membranes for the removal of high boiling organics from process water and wastewater by pervaporation
WO2016020708A1 (fr) Synthèse de polymères améliorée
WO2020045525A1 (fr) Soluté d'extraction et équipement de traitement d'eau
CN109912528B (zh) 一种类肽单体及其聚合物与应用
KR100314108B1 (ko) 아실기 함유 헥사아자이소우르치탄 유도체의 제조 방법
JPH05125037A (ja) 高純度２−アクリルアミド−２−メチルプロパンスルホン酸の製造方法
JP2009143827A (ja) アダマンチル（メタ）アクリレート類の製造方法
JPH0521616B2 (fr)
Alborzi et al. l-Lysine-derived optically active poly (hydrazide-imide) s: Synthesis, characterization and their application in removal of heavy metal ions
CN107721874B (zh) 一种采用微流场反应技术制备硝酸酯类化合物的方法
CN110590707B (zh) 一种含n-乙酰吗啉基官能团的聚环氧乙烷及制备方法
JPH0578291A (ja) アミノカルボン酸エステルの製造方法
KR910002674B1 (ko) 실릴케텐 아세탈의 아실화
JP2011052075A (ja) ポリ（ジアシルヒドラジン）の製造方法、及びポリ（ジアシルヒドラジン）
JP3403469B2 (ja) 光学活性なノルボルネン誘導体の重合体及び光学分割剤
WO2018042894A1 (fr) Composé nouveau de m-phénylenediamine et procédé de production d'un composé polymère au moyen de celui-ci
JP3904626B2 (ja) アクリル酸エステル誘導体の精製方法
FR2854894A1 (fr) 2-nitratoethyloxirane, poly(2-nitratoethyloxirane) et leur procede de preparation
Siran et al. Nutrient removal and biomass production from dairy farm liquid digestate treatment using microalga Chlorella vulgaris
Feyen et al. Poly (γ‐p‐nitrobenzyl‐l‐glulainate): synthetic aspects, sedimentation, and viscosity studies
CN115397832A (zh) 7-脱氢胆固醇或25-羟基-7-脱氢胆固醇或其oh保护形式的有机溶剂纳滤
JP2008127497A (ja) フェニレンエーテルオリゴマー体混合物の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19788973

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19788973

Country of ref document: EP

Kind code of ref document: A1