LU501613B1 - Phosphorus-free reverse osmosis scale inhibitor per-pamam and preparation methods thereof - Google Patents
Phosphorus-free reverse osmosis scale inhibitor per-pamam and preparation methods thereof Download PDFInfo
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- LU501613B1 LU501613B1 LU501613A LU501613A LU501613B1 LU 501613 B1 LU501613 B1 LU 501613B1 LU 501613 A LU501613 A LU 501613A LU 501613 A LU501613 A LU 501613A LU 501613 B1 LU501613 B1 LU 501613B1
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- pamam
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- scale inhibitor
- generation
- phosphorus
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- 239000002455 scale inhibitor Substances 0.000 title claims abstract description 96
- 229920000962 poly(amidoamine) Polymers 0.000 title claims abstract description 80
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 alcohol compound Chemical class 0.000 claims abstract description 43
- 239000003960 organic solvent Substances 0.000 claims abstract description 24
- 239000000047 product Substances 0.000 claims abstract description 24
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 20
- 238000006845 Michael addition reaction Methods 0.000 claims abstract description 19
- 238000005886 esterification reaction Methods 0.000 claims abstract description 16
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims abstract description 9
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 230000032050 esterification Effects 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 84
- 238000006243 chemical reaction Methods 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 23
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 20
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 6
- 150000004692 metal hydroxides Chemical class 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims description 4
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims description 3
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 4
- 229960004132 diethyl ether Drugs 0.000 claims 2
- BHMLFPOTZYRDKA-IRXDYDNUSA-N (2s)-2-[(s)-(2-iodophenoxy)-phenylmethyl]morpholine Chemical compound IC1=CC=CC=C1O[C@@H](C=1C=CC=CC=1)[C@H]1OCCNC1 BHMLFPOTZYRDKA-IRXDYDNUSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 31
- 230000005764 inhibitory process Effects 0.000 abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 11
- 239000011574 phosphorus Substances 0.000 abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 241000195493 Cryptophyta Species 0.000 abstract description 3
- 230000001580 bacterial effect Effects 0.000 abstract description 3
- 238000009395 breeding Methods 0.000 abstract description 3
- 230000001488 breeding effect Effects 0.000 abstract description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 235000010216 calcium carbonate Nutrition 0.000 abstract 1
- 229910052882 wollastonite Inorganic materials 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000002390 rotary evaporation Methods 0.000 description 9
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 229910001424 calcium ion Inorganic materials 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 238000004821 distillation Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000002024 ethyl acetate extract Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 229940087646 methanolamine Drugs 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000412 dendrimer Substances 0.000 description 2
- 229920000736 dendritic polymer Polymers 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- RXXCIBALSKQCAE-UHFFFAOYSA-N 3-methylbutoxymethylbenzene Chemical compound CC(C)CCOCC1=CC=CC=C1 RXXCIBALSKQCAE-UHFFFAOYSA-N 0.000 description 1
- 229910004762 CaSiO Inorganic materials 0.000 description 1
- 102100024482 Cell division cycle-associated protein 4 Human genes 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 101000980898 Homo sapiens Cell division cycle-associated protein 4 Proteins 0.000 description 1
- URWIWRCHIPAGBL-UHFFFAOYSA-N OCC1OP(=O)OP(=O)O1 Chemical compound OCC1OP(=O)OP(=O)O1 URWIWRCHIPAGBL-UHFFFAOYSA-N 0.000 description 1
- MDBVZFGSKMWJFD-UHFFFAOYSA-N OP(O)=O.OP(O)(O)=O Chemical compound OP(O)=O.OP(O)(O)=O MDBVZFGSKMWJFD-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002197 Sodium polyaspartate Polymers 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- ZKLNROBMVMIKKU-UHFFFAOYSA-N [K].[K].[K].[K].[K].[K].NCCCCCCN Chemical compound [K].[K].[K].[K].[K].[K].NCCCCCCN ZKLNROBMVMIKKU-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- DEGAKNSWVGKMLS-UHFFFAOYSA-N calcein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(CN(CC(O)=O)CC(O)=O)=C(O)C=C1OC1=C2C=C(CN(CC(O)=O)CC(=O)O)C(O)=C1 DEGAKNSWVGKMLS-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229960002378 oftasceine Drugs 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
-
- 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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (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)
Abstract
The disclosure belongs to field of water treatment chemicals, and specifically involves a phosphorus-free reverse osmosis scale inhibitor PER-PAMAM and preparation methods thereof. Performing a Michael addition reaction between pentaerythritol and acrylonitrile in alkaline environment, performing an esterification reaction between the Michael addition reaction product and alcohol compound in acidic condition, and reacting the esterification product with diamine compound in organic solvent to obtain a 1.0 generation scale inhibitor PER-PAMAM; and reacting 1.0 generation scale inhibitor PER-PAMAM with unsaturated fatty acid ester in organic solvent; and reacting the product with diamine compound in organic solvent to obtain 2.0 generation scale inhibitor PER-PAMAM. The chemical of the invention has small dosage and does not contain phosphorus to avoid serious bacterial and algae breeding problems; and it has excellent scale inhibition performance for CaCO3 scale and CaSiO3 scale; and the disclosure also provides preparation methods thereof without "three-waste" discharges throughout production process.
Description
BL-5380
PHOSPHORUS-FREE REVERSE OSMOSIS SCALE INHIBITOR PER-PAMAM 10501613
AND PREPARATION METHODS THEREOF
[01] The disclosure belongs to field of water treatment chemicals, and specifically involves a phosphorus-free reverse osmosis scale inhibitor PER-PAMAM and preparation methods thereof.
[02] It is well known that the pollution and lack of water resources seriously restricts the sustainable development of China. Circulating cooling water accounts for a large proportion of industrial water with the continuous development of economic society, so the circulation of cooling water has become the main way to save water. Due to the recycling of industrial cooling water, the concentration of inorganic ions such as Ca””, Mg?*, CO3”, SO4” and silicates in water increases gradually with the continuous evaporation and concentration of water, and the deposition of insoluble salts and scale in large amount affects the working efficiency and service life of reverse osmosis membranes. In inorganic scale, the deposition of silica and silicates is an extremely painful problem. Since the silica scale is hard in texture, it is difficult to remove once formed. Although adding hydrofluoric acid can effectively remove silica scale, this method will seriously reduce the service life of reverse osmosis membrane and bring great disadvantages to industrial production.
[03] In recent years, scale inhibitors have been widely used due to their advantages such as good synergistic effect, scale inhibition performance and less environmental pollution, and adding scale inhibitors to circulating cooling water is undoubtedly a simple, efficient, green and inexpensive scale inhibition method in order to reduce the formation of silica scale. However, most of the common scale inhibitors in the market are phosphorus-containing, and large-scale use causes water eutrophication and environmental damage.
[04] The components of the reverse osmosis membrane scale inhibitor disclosed in Chinese patent CN 101352655 are as follows by weight percentage: 25-50% organic phosphonic acid, 20-40% sulphonate copolymer, 5-15% pH regulator, and the balance deionized water. The components of the reverse osmosis membrane scale inhibitor disclosed in Chinese patent CN 102167451 A are as follows by weight percentage: 5-15% sodium polyepoxysuccinate, 5-15% sodium polyaspartate, 3-10% polymaleic acid, 1-5% 2-phosphonobutane-1, 2, 4-tricarboxylic acid, 8-15% hexapotassium hexamethylenediamine tetramethyl phosphate and polyamidoamine with hexamethylene diamine as the core, and the balance being water. These scale inhibitors can effectively control silica scale and calcium scale but they contain organic phosphonates, which are easy to hydrolyze and cause water eutrophication and environmental pollution. Chinese patent CN 102585196 A discloses a method for synthesizing a scale and corrosion inhibitor sodium polyepoxysuccinate, and the sodium polyepoxysuccinate can well control calcium scale, but the scale inhibiting effect on silica scale is not ideal.
[05] In view of the deficiencies of the prior art, the purpose of the present disclosure is to provide a phosphorus-free reverse osmosis scale inhibitor PER-PAMAM, which has a low dosage, does not contain phosphorus compared with traditional organic phosphonic acid 1
BL-5380 (phosphate) scale inhibitors, does not have the problem of excessive phosphorus discharge in concentrated water, and also does not provide nutrients for microorganisms in the membrane, LUS01613 so as to avoid causing serious bacterial and algae breeding problems; and it has excellent scale inhibition performance for CaCO; and CaSiO; scale. The present disclosure also provides preparation methods thereof, wherein the whole production process has no "three wastes" discharged, and has good economic benefits and wide social benefits.
[06] According to the phosphorus-free reverse osmosis scale inhibitor PER-PAMAM of the present disclosure, performing a Michael addition reaction between pentaerythritol and acrylonitrile in alkaline environment, performing an esterification reaction between the Michael addition reaction product and alcohol compound in acidic condition, and reacting the esterification reaction product with diamine compound in organic solvent to obtain a 1.0 generation scale inhibitor PER-PAMAM.
[07] Pentaerythritol has four hydroxyl functional groups in the molecular structure, and the structure is completely symmetrical, which is very suitable for constructing dendritic macromolecules. At present, there are relatively few studies on novel dendrimer silica scale inhibitors based on pentaerythritol and derivatives thereof as the core. Compared with the traditional organic phosphonic acid (phosphate) scale inhibitor, the dosage of the chemical is less and does not contain phosphorus, and there is no problem of excessive phosphorus discharge in concentrated water.
[08] Wherein: the molar ratio of pentaerythritol to acrylonitrile is 1:4-1:7; and the molar ratio of the Michael addition reaction product to alcohol compound is 1:8-1:12; and the molar ratio of the esterification product to diamine compound is 1:14-1:18.
[09] Preferably, reacting the 1.0 generation scale inhibitor PER-PAMAM with unsaturated fatty acid ester in organic solvent; and reacting the reaction product with diamine compound in organic solvent to obtain 2.0 generation scale inhibitor PER-PAMAM. The scale inhibitor of 2.0 generation has more amine end groups and better scale inhibition performance compared with that of 1.0 generation.
[10] The molar ratio of the 1.0 generation scale inhibitor PER-PAMAM to the unsaturated fatty acid ester is 1:22-1:28, and the molar ratio of the reaction product to the diamine compound is 1:30-1:36.
[11] Wherein:
[12] performing the Michael addition reaction in a two-phase system of aqueous metal hydroxide solution and organic solvent; and the metal hydroxide is alkali metal hydroxide or alkaline earth metal hydroxide; the alkali metal hydroxide is lithium hydroxide, potassium hydroxide or sodium hydroxide; the alkaline earth metal hydroxide is calcium hydroxide, strontium hydroxide or barium hydroxide; and the organic solvent is one or more of branched or unbranched alkane, alkyl-substituted aromatic solvent, alcohol or ether which is water- immiscible or partially water-miscible, preferably the organic solvent is one or more of methanol, ethanol, butanediol, benzene, toluene, xylene, 1,4-dioxane, diethyl ether, tetrahydrofuran, dichloromethane, or triethanolamine. Side reactions of acrylonitrile can be suppressed by using this two-phase system.
[13] The temperature of the Michael addition reaction is 0 °C-70 °C and the time is 10-12 hours; and the temperature of the esterification reaction is 50 °C-90 °C and the time is 2-6 hours. 2
BL-5380
[14] The alcohol compound is methanol, ethanol or propanol; and the diamine compound is ethylenediamine, propane diamine or butanediamine. LU501613
[15] The unsaturated fatty acid ester is methyl acrylate or methyl methacrylate, containing unsaturated bonds and ester groups, capable of both Michael addition and amidation reactions.
[16] According to a preparation method of the phosphorus-free reverse osmosis scale inhibitor PER-PAMAM of the present disclosure, performing a Michael addition reaction between pentaerythritol and acrylonitrile in alkaline environment, performing an esterification reaction between the Michael addition reaction product and alcohol compound in acidic condition, and reacting the esterification reaction product with diamine compound in organic solvent to obtain a 1.0 generation scale inhibitor PER-PAMAM in the preparation method of the phosphorus-free reverse osmosis scale inhibitor PER-PAMAM.
[17] Preferably, a preparation method of the phosphorus-free reverse osmosis scale inhibitor
PER-PAMAM according to the disclosure comprises the following steps:
[18] (1) Performing the Michael addition reaction between pentaerythritol and acrylonitrile in a two-phase system of aqueous metal hydroxide solution and organic solvent, and controlling the pH of the whole system at 8-10;
[19] (2) Mixing the reaction product obtained in step (1) with alcohol compound, introducing HCI gas, and the pH value is 2-3 to perform an esterification reaction;
[20] (3) Reacting the reaction product obtained in step (2) with diamine compound in organic solvent to obtain 1.0 generation scale inhibitor PER-PAMAM,;
[21] (4) Reacting the 1.0 generation scale inhibitor PER-PAMAM with unsaturated fatty acid ester in organic solvent.
[22] (5) Reacting the reaction product obtained in step (4) with diamine compound in organic solvent; and obtaining 2.0 generation scale inhibitor PER-PAMAM.
[23] More preferably, a preparation method of the phosphorus-free reverse osmosis scale inhibitor PER-PAMAM according to the disclosure comprises the following steps:
[24] (1) Adding pentaerythritol and acrylonitrile into a three-neck flask in the molar ratio of 1:4-1:7, and creating alkaline environment using 40% KOH aqueous solution, using 1,4- dioxane as a solvent, controlling the pH of the whole system at 8-10, and performing the reaction at room temperature for 10-12 hours and purifying to obtain an intermediate tetranitrile.
[25] (2) Adding the intermediate tetranitrile and methanol into a four-neck flask in the molar ratio of 1:8-1:12, introducing HCI gas, the pH value is 2-3, and performing the reaction at 50 °C- 90 °C for 2-6 hours and purifying to obtain 0.5 generation PER-PAMAM scale inhibitor.
[26] (3) Adding 0.5 generation PER-PAMAM scale inhibitor and ethylenediamine into a three-neck flask in the molar ratio of 1:14-1:18, using methanol as solvent, reacting at room temperature for 10-12 hours and purifying to obtain 1.0 generation PER-PAMAM scale inhibitor. 3
BL-5380
[27] (4) Adding 1.0 generation PER-PAMAM scale inhibitor and methyl acrylate into a three-neck flask in the molar ratio of 1:22-1:28, using methanol as solvent, and reacting at room LU501613 temperature for 10-12 hours and purifying to obtain 1.5 generation PER-PAMAM scale inhibitor.
[28] (5) Adding the 1.5 generation PER-PAMAM scale inhibitor and ethylenediamine into a three-neck flask in the molar ratio of 1:30-1:36, using methanol as solvent, and reacting at room temperature for 10-12 hours and purifying to obtain 2.0 generation PER-PAMAM scale inhibitor.
[29] The present disclosure has the following advantages compared to the prior art:
[30] (1) The present disclosure provides a novel non-phosphorus environment-friendly reverse osmosis scale inhibitor, comprising a 1.0 generation scale inhibitor PER-PAMAM and a 2.0 generation scale inhibitor PER-PAMAM, which are both novel polyamidoamine dendrimer scale inhibitors for scale treatment of water quality, and compared with traditional organic phosphonic acid (salt) scale inhibitors, the dosage of the scale inhibitor is less and does not contain phosphorus, is biodegradable, and there is no problem of excessive phosphorus discharge in concentrated water, and also does not provide nutrients for microorganisms in the membrane, so as to avoid causing serious bacterial and algae breeding problems.
[31] (2) The scale inhibitor of the present disclosure has a more excellent scale inhibition performance for CaCO; scale and CaSiOs scale in addition to the excellent scale inhibition performance for these conventional scales such as calcium scale. The phosphorus-free reverse osmosis scale inhibitor PER-PAMAM of the present disclosure has a higher scale inhibition effect at a lower dosage than the disclosed scale inhibitor.
[32] (3) The preparation methods provided by the present disclosure have no "three-waste" discharge in the whole production process, and the scale inhibition process for treating complex water quality is simple, small dosage in use, low in cost, good in effect, and has very good economic benefits and wide social benefits; it has the advantages of good scale inhibition performance, green pollution-free and low price.
[33] The disclosure will be further described in detail with reference to the accompanying drawings and embodiments.
Embodiment 1
[34] 20 g pentaerythritol and acrylonitrile in the molar ratio of 1:6 were added into a three- neck flask, alkaline environment was created using 40% KOH aqueous solution, 1,4-dioxane was used as solvent, the pH of the whole system was controlled to 9, magnetic stirring was performed, and acrylonitrile was slowly added dropwise via a constant pressure addition funnel.
The reaction was maintained at room temperature for 10 hours after the addition. The reaction mixture was dissolved in appropriate amount of dichloromethane and extracted several times with small amount of deionized water after completion of the reaction. The organic phase was dried using anhydrous sodium sulphate, and then the solvents DCM, 1,4-dioxane and excess acrylonitrile were removed by rotary distillation to give tetranitrile in 85% yield.
[35] 20 g tetranitrile and methanol were added into a four-neck flask in the molar ratio of 4
BL-5380 1:10 with the temperature controlled at 85 °C, reflux was conducted, HCI gas was introduced, the pH value was 2.5, and the reaction was stirred for 4 hours. Excess methanol was removed LU501613 by rotary evaporation, washed with water, added ethyl acetate, extracted and separated. The ethyl acetate extract was then washed with deionized water, dried using anhydrous sodium sulphate, filtered and concentrated to obtain 0.5 generation PER-PAMAM scale inhibitor in 88% yield.
[36] 20 g 0.5 generation product and methanol were added into a three-neck flask, ethylenediamine was added dropwise into the flask in the molar ratio of the 0.5 generation product to ethylenediamine 1:18, after the completion of the dropwise addition, the reaction was carried out at room temperature for 10 hours, and after the reaction was completed, rotary distillation was completed to remove excess methanol and ethylenediamine to obtain 1.0 generation PER-PAMAM scale inhibitor in 87% yield.
[37] 20 g 1.0 generation product and methanol were added into a three-neck flask, and methyl acrylate was added dropwise in the molar ratio of 1.0 generation product to methyl acrylate 1:26, and reacted at room temperature for 10 hours; after the reaction was completed, rotary evaporation purification was performed to obtain 1.5 generation PER-PAMAM scale inhibitor in 89% yield.
[38] Methanol and 20 g 1.5 generation product were added into a three-neck flask, and ethylenediamine was added in the molar ratio of 1.5 generation product to ethylenediamine 1:32, and reacted at room temperature for 10 hours. After completion of the reaction, it was purified by rotary evaporation to obtain 2.0 generation PER-PAMAM scale inhibitor in 90% yield.
Embodiment 2
[39] 20 g pentaerythritol and acrylonitrile were added into a three-neck flask in the molar ratio of 1:6, alkaline environment was created with 40% KOH aqueous solution, 1,4-dioxane was used as solvent, the pH of the whole system was controlled to 9, magnetic stirring was performed, and acrylonitrile was slowly added dropwise via a constant pressure addition funnel.
The reaction was maintained at room temperature for 12 hours after the addition. The reaction mixture was dissolved in appropriate amount of dichloromethane and extracted several times with small amount of deionized water after completion of the reaction. The organic phase was dried using anhydrous sodium sulphate, and then the solvents DCM, 1,4-dioxane and excess acrylonitrile were removed by rotary distillation to give tetranitrile in 90% yield.
[40] 20 g tetranitrile and methanol were added into a four-neck flask in the molar ratio of 1:10 with the temperature controlled at 85 °C, reflux was conducted, HCI gas was introduced, the pH value was 2.5, and the reaction was stirred for 6 hours. Excess methanol was removed by rotary evaporation, washed with water, added ethyl acetate, extracted and separated, and then the ethyl acetate extract was washed with deionized water, dried using anhydrous sodium sulphate, filtered and concentrated to obtain 0.5 generation PER-PAMAM scale inhibitor in 89% yield.
[41] 20 g 0.5 generation product and methanol were added into a three-neck flask, ethylenediamine was added dropwise into the flask in the molar ratio of the 0.5 generation product to ethylenediamine 1:18, after the completion of the dropwise addition, the reaction was carried out at room temperature for 12 hours, and after the reaction was completed, rotary distillation was completed to remove excess methanol and ethylenediamine to obtain 1.0
BL-5380 generation PER-PAMAM scale inhibitor in 95% yield.
LU501613
[42] 20 g 1.0 generation product and methanol were added into a three-neck flask, and methyl acrylate was added dropwise in the molar ratio of 1.0 generation product to methyl acrylate 1:26, and reacted at room temperature for 12 hours; after the reaction was completed, rotary evaporation purification was performed to obtain 1.5 generation PER-PAMAM scale inhibitor in 97% yield.
[43] Methanol and 20 g 1.5 generation product were added into a three-neck flask, and ethylenediamine was added in the molar ratio of 1.5 generation product to ethylenediamine 1:32, and reacted at room temperature for 12 hours. After completion of the reaction, it was purified by rotary evaporation to obtain 2.0 generation PER-PAMAM scale inhibitor in 96% yield.
Embodiment 3
[44] 20 g pentaerythritol and acrylonitrile were added into a three-neck flask in the molar ratio of 1:6, alkaline environment was created with 40% KOH aqueous solution, 1,4-dioxane was used as solvent, the pH of the whole system was controlled to 9, magnetic stirring was performed, and acrylonitrile was slowly added dropwise via a constant pressure addition funnel.
The reaction was maintained at 50 °C for 12 hours after the addition. The reaction mixture was dissolved in appropriate amount of dichloromethane and extracted several times with small amount of deionized water after completion of the reaction. The organic phase was dried using anhydrous sodium sulphate, and then the solvents DCM, 1,4-dioxane and excess acrylonitrile were removed by rotary distillation to give tetranitrile in 80% yield.
[45] 20 g tetranitrile and methanol were added into a four-neck flask in the molar ratio of 1:10 with the temperature controlled at 85 °C, reflux was conducted, HCI gas was introduced, and the reaction was stirred for 6 hours. Excess methanol was removed by rotary evaporation, washed with water, added ethyl acetate, extracted and separated. The ethyl acetate extract was then washed with deionized water, dried using anhydrous sodium sulphate, filtered and concentrated to obtain 0.5 generation PER-PAMAM scale inhibitor in 89% yield.
[46] 20 g of 0.5 generation product and methanol were added into a three-neck flask.
Ethylenediamine was added dropwise into the flask in the molar ratio of the 0.5 generation product to ethylenediamine 1:18, after the completion of the dropwise addition, the reaction was carried out at 50 °C for 12 hours, and rotary distillation was completed to remove excess methanol and ethylenediamine to obtain 1.0 generation PER-PAMAM scale inhibitor in 82% yield.
[47] 20 g 1.0 generation product and methanol were added into a three-neck flask, and methyl acrylate was added dropwise in the molar ratio of 1.0 generation product to methyl acrylate 1:26, and reacted at 50 °C for 12 hours; after the reaction was completed, rotary evaporation purification was performed to obtain 1.5 generation PER-PAMAM scale inhibitor in 83% yield.
[48] Methanol and 20 g 1.5 generation product were added into a three-neck flask, and ethylenediamine was added in the molar ratio of 1.5 generation product to ethylenediamine 1:32, and reacted at 50 °C for about 12 hours. After completion of the reaction, it was purified by rotary evaporation to obtain 2.0 generation PER-PAMAM scale inhibitor in 85% yield. 6
BL-5380
[49] The performance of scale inhibitors prepared in embodiments 1-3 was tested:
LU501613
[50] 1. Determination of silica scale inhibition performance
[51] Static silicate inhibition method: Sample preparation process is as follows: deionized water was used to prepare the sodium silicate solution with SiO, concentration of 600 mg/L, and appropriate amount of scale inhibitor was added, then hydrochloric acid and sodium hydroxide were used to adjust the pH value of the solution to 7.0+0.1, and then a certain amount of calcium chloride was added to make the calcium ion concentration in the solution to 500 mg/L. Then the pH value was adjusted to 7.0+0.1. All samples prepared in this way were placed in a multihole thermostatic water bath, the temperature was set at 40 °C. À certain amount of water samples were filtered at regular intervals, and the content of silicate ions was determined by spectrophotometry and the scale inhibition rate was calculated. Calculation formula:
E, = Pı7Po 100%
P -Po
Wherein: Er-- Silica scale inhibition rate, % p1 -- Content of silicate ion in dosing solution, mg/L po --Content of silicate ion in blank solution, mg/L p --Content of initial silicate ion in solution, mg/L.
[52] The amount of scale inhibitor added and the test results are shown in Table 1.
[53] 2. Determination of calcium carbonate scale inhibition performance
[54] 3 mL of 40 g/L. calcium chloride solution was sequentially added into a 500 mL volumetric flask, 5 mL of 48.8 g/L. sodium bicarbonate solution and suitable amount of scale inhibitor, and deionized water was added to constant volume and shake well. The volumetric flasks were placed into a multihole thermostatic water bath, the temperature was set at 80 °C, heated for 10 hours, then the volumetric flasks were taken out to cool naturally, then the upper clear liquid was drawn for analysis and the content of calcium ion was determined. A blank control test was also carried out.
[55] A pipette was used to measure 10 mL of test solution, 50 mL of deionized water and 5 mL of 20% potassium hydroxide solution were successively added into the conical flask; and the solution showed green after adding appropriate amount of calcein indicator into the conical flask, and then EDTA standard solution was used for titration; it can be found that the green gradually disappears and it is the end point of titration when the green completely disappeared and the purple red happened to appear. The concentration X (mg/L) of calcium ion (Ca””) can be calculated according to the following formula: x- Crpra XV, x40.48x1000
V
Wherein: X-Concentration of calcium ion (Ca**), mg/L 7
BL-5380
C-Concentration of EDTA standard solution, mol/L
LU501613
V1-Volume of EDTA solution consumed, ml 40.48-Molar mass of calcium ion, g/mol.
[56] Calculation method for the scale inhibition rate 0 of calcium carbonate: 0 =[(Ca1**- Car”*)/( Cao”*-Caz*)] x100%
Wherein: Cao”*-Concentration of calcium ion before scale inhibition reaction, mg/L
Ca1*”*-Remaining concentration of calcium ion after scale inhibition reaction with the presence of scale inhibitor, mg/L
Ca»*”*-Remaining concentration of calcium ion after scale formation in blank test, mg/L,
The amount of scale inhibitor added and test results are shown in Table 1.
[57] Comparative Embodiment: The scale inhibition effect of HEDP (hydroxyethylidene diphosphonate) used alone.
Table 1 Calculation results of scale inhibition performance test
Adding Scale Adding Scale
Let amount of inhibition amount of | Inhibition rate
Scale inhibitor Cale inhibitor Tate Of SiOz scale inhibitor Of CaCOs (mg/L) (%) (mg/L) (%) 1.0 generation 60 78.9 18 28.6 . scale inhibitor ; ;
Embodiment 1 ; 2.0 generation 60 85.6 18 03.7 scale inhibitor 1.0 generation 60 81.7 18 02.8 . scale inhibitor
Embodiment 2 ; 2.0 generation 60 88.7 18 06.7 scale inhibitor 1.0 generation 60 75.3 18 85.3 . scale inhibitor
Embodiment 3 ; 2.0 generation 60 83.5 18 89.7 scale inhibitor 8
BL-5380
Comparative HEpp 60 478 20 78.2 LU501613
[58] As can be seen from Table 1, the scale inhibitor of the present disclosure has excellent scale inhibition performance against both silica scale and calcium scale. Meanwhile, the phosphorus-free reverse osmosis scale inhibitor PER-PAMAM of the present disclosure has a higher scale inhibition effect at a lower dosage than other disclosed scale inhibitors.
[59] Furthermore, the novel reverse osmosis scale inhibitor PER-PAMAM of the present disclosure does not contain phosphorus and has no problem of excessive phosphorus discharge in concentrated water and is an environment-friendly reverse osmosis scale inhibitor. 9
Claims (10)
1. À phosphorus-free reverse osmosis scale inhibitor PER-PAMAM, characterized in that: performing a Michael addition reaction between pentaerythritol and acrylonitrile in alkaline environment, performing an esterification reaction between the Michael addition reaction product and alcohol compound in acidic condition, and reacting the esterification reaction product with diamine compound in organic solvent to obtain a 1.0 generation scale inhibitor PER-PAMAM.
2. The phosphorus-free reverse osmosis scale inhibitor PER-PAMAM according to claim 1, characterized in that: the molar ratio of pentaerythritol to acrylonitrile is 1:4-1:7; and the molar ratio of the Michael addition reaction product to alcohol compound is 1:8-1:12; and the molar ratio of the esterification product to diamine compound is 1:14-1:18.
3. The phosphorus-free reverse osmosis scale inhibitor PER-PAMAM according to claim 1, characterized in that: reacting the 1.0 generation scale inhibitor PER-PAMAM with unsaturated fatty acid ester in organic solvent; and reacting the reaction product with diamine compound in organic solvent to obtain 2.0 generation scale inhibitor PER-PAMAM.
4. The phosphorus-free reverse osmosis scale inhibitor PER-PAMAM according to claim 3, characterized in that: the molar ratio of the 1.0 generation scale inhibitor PER-PAMAM to the unsaturated fatty acid ester is 1:22-1:28, and the molar ratio of the reaction product to the diamine compound is 1:30-1:36.
5. The phosphorus-free reverse osmosis scale inhibitor PER-PAMAM according to claim 1, characterized in that: performing the Michael addition reaction in a two-phase system of aqueous metal hydroxide solution and organic solvent; wherein the metal hydroxide is alkali metal hydroxide or alkaline earth metal hydroxide; the alkali metal hydroxide is lithium hydroxide, potassium hydroxide or sodium hydroxide; the alkaline earth metal hydroxide is calcium hydroxide, strontium hydroxide or barium hydroxide; and the organic solvent is one or more of methanol, ethanol, butanediol, benzene, toluene, xylene, 1,4-dioxane, diethyl ether, tetrahydrofuran, dichloromethane, or triethanolamine.
6. The phosphorus-free reverse osmosis scale inhibitor PER-PAMAM according to claim 1, characterized in that: the temperature of the Michael addition reaction is 0 °C-70 °C and the time is 10-12 hours; and the temperature of the esterification reaction is 50 °C-90 °C and the time is 2-6 hours.
7. The phosphorus-free reverse osmosis scale inhibitor PER-PAMAM according to claim 1 or 3, characterized in that: the alcohol compound is methanol, ethanol or propanol; and the diamine compound is ethylenediamine, propane diamine or butanediamine.
8. The phosphorus-free reverse osmosis scale inhibitor PER-PAMAM according to claim 3, characterized in that: the unsaturated fatty acid ester is methyl acrylate or methyl methacrylate.
9. A preparation method of the phosphorus-free reverse osmosis scale inhibitor PER- PAMAM according to any one of claims 1 to 6, characterized in that: performing a Michael addition reaction between pentaerythritol and acrylonitrile in alkaline environment, performing an esterification reaction between the Michael addition reaction product and alcohol compound
BL-5380 in acidic condition, and the esterification product reacts with diamine compound in organic solvent to obtain a 1.0 generation scale inhibitor PER-PAMAM. LU501613
10. The preparation method of the phosphorus-free reverse osmosis scale inhibitor PER- PAMAM according to claim 9, characterized in that, it comprises the following steps: (1) Performing the Michael addition reaction between pentaerythritol and acrylonitrile in a two-phase system of aqueous metal hydroxide solution and organic solvent, and controlling the pH of the whole system at 8-10; (2) Mixing the reaction product obtained in step (1) with alcohol compound, introducing HCI gas, and the pH value is 2-3 to perform an esterification reaction; (3) Reacting the reaction product obtained in step (2) with diamine compound in organic solvent to obtain 1.0 generation scale inhibitor PER-PAMAM,; (4) Reacting the 1.0 generation scale inhibitor PER-PAMAM with unsaturated fatty acid ester in organic solvent. (5) Reacting the reaction product obtained in step (4) with diamine compound in organic solvent; and obtaining 2.0 generation scale inhibitor PER-PAMAM. 11
BL-5380 LU501613 ANSPRÜCHE
1. Phosphorfreier Umkehrosmose-Kesselsteininhibitor PER-PAMAM, dadurch gekennzeichnet: Durchführen einer Michael-Additionsreaktion zwischen Pentaerythrit und Acrylnitril in einer alkalischen Umgebung, Durchführen einer Veresterungsreaktion zwischen dem Michael-Additionsreaktionsprodukt und einer Alkoholverbindung in einem sauren Zustand und Reagieren des Veresterungsreaktionsprodukts mit einer Diaminverbindung in einem organischen Lôsungsmittel, um einen Kesselsteininhibitor PER-PAMAM der Generation 1.0 zu erhalten.
2. Phosphorfreier Umkehrosmose-Kesselsteininhibitor PER-PAMAM nach Anspruch 1, dadurch gekennzeichnet, dass: das Molverhältnis von Pentaerythrit zu Acrylnitril 1:4—1:7 beträgt und das Molverhéltnis des Michael- Additionsreaktionsprodukts zu der Alkoholverbindung 1:8—1:12 beträgt und das Molverhältnis des Veresterungsprodukts zu der Diaminverbindung 1:14—1:18 betragt.
3. Phosphorfreier Umkehrosmose-Kesselsteininhibitor PER-PAMAM nach Anspruch 1, dadurch gekennzeichnet: Reagieren des Kesselsteininhibitors PER- PAMAM der Generation 1.0 mit einem ungesâttigten Fettsäureester in einem organischen Lösungsmittel und Reagieren des Reaktionsprodukts mit einer Diaminverbindung in einem organischen Lösungsmittel, um einen Kesselsteininhibitor PER-PAMAM der Generation 2.0 zu erhalten.
4. Phosphorfreier Umkehrosmose-Kesselsteininhibitor PER-PAMAM nach Anspruch 3, dadurch gekennzeichnet, dass: das Molverhältnis des Kesselsteininhibitors PER-PAMAM der Generation 1.0 zu dem ungesattigten Fettsäureester 1:22—1:28 beträgt und das Molverhaltnis des Reaktionsprodukts zu der Diaminverbindung 1:30—1:36 betragt. 1
BL-5380 LU501613
5. Phosphorfreier Umkehrosmose-Kesselsteininhibitor PER-PAMAM nach Anspruch 1, dadurch gekennzeichnet: Durchführen der Michael- Additionsreaktion in einem Zwei-Phasen-System von einer wässrigen Metallhydroxidlésung und einem organischen Lösungsmittel; wobei das Metallhydroxid ein Alkalimetallhydroxid oder ein Erdalkalimetallhydroxid ist; das Alkalimetallhydroxid Lithiumhydroxid, Kaliumhydroxid oder Natriumhydroxid ist; das Erdalkalimetallhydroxid Calciumhydroxid, Strontiumhydroxid oder Bariumhydroxid ist und es sich bei dem organischen Lösungsmittel um eines oder mehrere von Methanol, Ethanol, Butandiol, Benzol, Toluol, Xylol, 1,4-Dioxan, Diethylether, Tetrahydrofuran, Dichlormethan oder Triethanolamin handelt.
6. Phosphorfreier Umkehrosmose-Kesselsteininhibitor PER-PAMAM nach Anspruch 1, dadurch gekennzeichnet, dass: die Temperatur der Michael- Additionsreaktion 0 °C — 70 °C beträgt und die Zeit 10—12 Stunden beträgt und die Temperatur der Veresterungsreaktion 50 °C — 90 °C beträgt und die Zeit 2— 6 Stunden beträgt.
7. Phosphorfreier Umkehrosmose-Kesselsteininhibitor PER-PAMAM nach Anspruch 1 oder 3, dadurch gekennzeichnet, dass: die Alkoholverbindung Methanol, Ethanol oder Propanol ist und die Diaminverbindung Ethylendiamin, Propandiamin oder Butandiamin ist.
8. Phosphorfreier Umkehrosmose-Kesselsteininhibitor PER-PAMAM nach Anspruch 3, dadurch gekennzeichnet, dass: der ungesättigte Fettsäureester Methylacrylat oder Methylmethacrylat ist.
9. Herstellungsverfahren für den phosphorfreien Umkehrosmose- Kesselsteininhibitor PER-PAMAM nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet: Durchführen einer Michael-Additionsreaktion zwischen Pentaerythrit und Acrylnitril in einer alkalischen Umgebung, Durchführen einer Veresterungsreaktion zwischen dem Michael-Additionsreaktionsprodukt und einer Alkoholverbindung in einem sauren Zustand, und wobei das 2
BL-5380 LU501613 Veresterungsprodukt mit einer Diaminverbindung in einem organischen Lösungsmittel reagiert, um einen Kesselsteininhibitor PER-PAMAM der Generation 1.0 zu erhalten.
10. Herstellungsverfahren für den phosphorfreien = Umkehrosmose- Kesselsteininhibitor PER-PAMAM nach Anspruch 9, dadurch gekennzeichnet, dass es die folgenden Schritte umfasst: (1) Durchführen der Michael-Additionsreaktion zwischen Pentaerythrit und Acrylnitril in einem Zwei-Phasen-System von einer wässrigen Metallhydroxidldsung und einem organischen Lösungsmittel und Regulieren des pH-Werts des gesamten Systems auf 8-10; (2) Mischen des in Schritt (1) erhaltenen Reaktionsprodukts mit einer Alkoholverbindung, Einbringen von HCI-Gas, und wobei der pH-Wert 2-3 beträgt, um eine Veresterungsreaktion durchzuführen; (3) Reagieren des in Schritt (2) erhaltenen Reaktionsprodukts mit einer Diaminverbindung in einem organischen Lösungsmittel, um einen Kesselsteininhibitor PER-PAMAM der Generation 1.0 zu erhalten; (4) Reagieren des Kesselsteininhibitors PER-PAMAM der Generation 1.0 mit einem ungesâttigten Fettsäureester in einem organischen Lösungsmittel; (5) Reagieren des in Schritt (4) erhaltenen Reaktionsprodukts mit einer Diaminverbindung in einem organischen Lösungsmittel und Erhalten eines Kesselsteininhibitors PER-PAMAM der Generation 2.0. 3
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