CN110746526A - Sulfydryl functionalized polyvinyl alcohol and preparation method and application thereof - Google Patents
Sulfydryl functionalized polyvinyl alcohol and preparation method and application thereof Download PDFInfo
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- polyvinyl alcohol
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- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 45
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 11
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 11
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 10
- 229930195729 fatty acid Natural products 0.000 claims abstract description 10
- 239000000194 fatty acid Substances 0.000 claims abstract description 10
- -1 mercapto fatty acid Chemical class 0.000 claims abstract description 9
- 238000005886 esterification reaction Methods 0.000 claims abstract description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 6
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 6
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229940125782 compound 2 Drugs 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229940005605 valeric acid Drugs 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 238000010511 deprotection reaction Methods 0.000 abstract description 2
- 238000011403 purification operation Methods 0.000 abstract description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 29
- 239000000047 product Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 3
- CFPHMAVQAJGVPV-UHFFFAOYSA-N 2-sulfanylbutanoic acid Chemical compound CCC(S)C(O)=O CFPHMAVQAJGVPV-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- SRVFFFJZQVENJC-IHRRRGAJSA-N aloxistatin Chemical compound CCOC(=O)[C@H]1O[C@@H]1C(=O)N[C@@H](CC(C)C)C(=O)NCCC(C)C SRVFFFJZQVENJC-IHRRRGAJSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 1
- JJWSNOOGIUMOEE-UHFFFAOYSA-N Monomethylmercury Chemical compound [Hg]C JJWSNOOGIUMOEE-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000008499 blood brain barrier function Effects 0.000 description 1
- 210000001218 blood-brain barrier Anatomy 0.000 description 1
- OSVHLUXLWQLPIY-KBAYOESNSA-N butyl 2-[(6aR,9R,10aR)-1-hydroxy-9-(hydroxymethyl)-6,6-dimethyl-6a,7,8,9,10,10a-hexahydrobenzo[c]chromen-3-yl]-2-methylpropanoate Chemical compound C(CCC)OC(C(C)(C)C1=CC(=C2[C@H]3[C@H](C(OC2=C1)(C)C)CC[C@H](C3)CO)O)=O OSVHLUXLWQLPIY-KBAYOESNSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000002485 urinary effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
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- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses sulfhydryl functionalized polyvinyl alcohol (formula I) and a preparation method thereof. The invention develops and optimizes esterification reaction of trityl protected mercapto fatty acid and polyvinyl alcohol, and then carries out deprotection and hydrolysis, thereby obtaining the highly-thiolated polyvinyl alcohol. The whole synthesis process route is efficient and simple, complicated purification operation is not needed, and the method has high industrial value and can be applied to removal of trace mercury in water.
Description
Technical Field
The invention relates to organic synthesis and wastewater treatment technologies, in particular to sulfydryl functionalized polyvinyl alcohol and a preparation method and application thereof.
Background
Mercury and its compounds are a persistent high pollutant, which has become a global environmental problem, and long-term mercury exposure can produce toxic effects on skin, lungs, liver, blood-brain barrier, urinary system and nervous system. In particular, methylmercury has high biological accumulation and biological amplification effect in the food chain and has extremely serious harm to human. Currently, the World Health Organization (WHO) has set the mercury limit of 1ng/L in the use water. Therefore, the development of mercury removal technology, especially the removal of trace mercury, is urgently needed.
The sulfydryl is a sulfur-containing group and has a high-efficiency mercury fixing function. The invention uses polyvinyl alcohol (PVA) as a carrier, develops a simple method to connect organic mercapto fatty acid to PVA, prepares the high mercapto functionalized polyvinyl alcohol, and can be applied to removing trace mercury in water. The method can realize high sulfhydrylation, selectively remove acetyl on PVA, improve the water solubility of the polymer, and has simple operation and higher industrial value.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the prior art, the invention provides sulfydryl functionalized polyvinyl alcohol and a preparation method thereof.
The technical scheme is as follows: the invention relates to mercapto-functionalized polyvinyl alcohol, which has a structure shown in formula I:
wherein R ═ H or
q is 1, 2, 3 or 4, and m and n are natural numbers of 1 to 1000.
That is, the branched chain is a fatty acid such as thioglycolic acid, propionic acid, butyric acid, valeric acid, etc.
The invention also discloses a preparation method of the sulfhydryl functionalized polyvinyl alcohol, and the synthetic route is as follows:
the method comprises the following steps:
(1) carrying out esterification reaction on polyvinyl alcohol 1 and trityl protected mercapto fatty acid 4 under the catalysis of EDCI and DMAP to obtain a compound 2;
(2) compound 2 is subjected to trityl removal by a TFA/water/trisisopyropyllane system and then to selective hydrolysis of the acetyl group by a sulfuric acid/methanol system to give thiol-functionalized polyvinyl alcohol 3.
In the step (1), the polyvinyl alcohol 1 contains acetyl or does not contain acetyl, and the solvent is DMF.
In the step (1), firstly, dissolving polyvinyl alcohol 1 in DMF, and then adding trityl-protected mercaptofatty acid 4 and a catalyst for reaction, wherein the dosage ratio of the polyvinyl alcohol 1 to the trityl-protected mercaptofatty acid 4 is 1:1 to 1.5, preferably 1: 1.3. Namely, 1 to 1.5equiv of a mercapto fatty acid 4 per equiv of a polyvinyl alcohol 1, preferably 1.3equiv of a mercapto fatty acid 4 per equiv of a polyvinyl alcohol 1.
In the step (1), the dosage of the EDCI catalyst is 1-1.5 times that of the trityl-protected mercaptofatty acid 4, and the dosage of the DMAP catalyst is 0.2-0.5 times that of the trityl-protected mercaptofatty acid 4.
Further, in the step (1), the trityl-protected mercaptofatty acid 4 is trityl-protected mercaptoacetic acid, propionic acid, butyric acid, or valeric acid.
In the step (2), the TFA/water/trisisopysulane system volume ratio is 8-12 vol: 0.5-2vol,: 0.4-0.8vol, preferably 10vol:1vol:0.6 vol.
In the step (2), the dosage ratio of the 0.3M sulfuric acid/methanol system is 8-12 vol: 3-6 vol.
After the reaction of the step (1) and the step (2), adding solvents such as acetonitrile, water, isopropanol, methanol, ethanol and the like to precipitate a product.
The esterification reaction temperature of the step (1) is 40-60 ℃, and the reaction time is 10-30 hours.
And (3) removing trityl in the step (2) and reacting at normal temperature for 1-3 hours, and reacting at 50-70 ℃ for 3 hours by hydrolysis of acetyl.
The use of the above-described mercapto-functionalized polyvinyl alcohols for mercury removal from water is also within the scope of the present invention.
Has the advantages that: the invention develops and optimizes esterification reaction of trityl protected mercapto fatty acid and polyvinyl alcohol, and then carries out deprotection and hydrolysis, thereby obtaining the highly-thiolated polyvinyl alcohol. The whole synthetic process route is efficient and simple, complicated purification operation is not needed, the industrial value is high, and the prepared sulfydryl functionalized polyvinyl alcohol can be used for removing trace mercury in water.
Drawings
FIG. 1 is a hydrogen spectrum of Compound 2 a;
figure 2 is a product 3a hydrogen spectrum.
Detailed Description
The present application will be described in detail with reference to specific examples.
Example 1
The invention provides a preparation method of high sulfydryl functionalized polyvinyl alcohol, which comprises the following synthetic route:
(1) synthesis of Compound 2a
Commercial PVA 1a (50g,. about.89% acetyl hydrolyzed, MW. about.31000 Da) was added to DMF (850mL), the reaction was raised to 95 ℃ and stirred for one hour until PVA was completely dissolved, then cooled to 50 ℃ and trityl protected mercaptopropionic acid 4a (0.56g, 1.3equiv), EDCI (0.34g,1.1equiv) and DMAP (60mg,0.3equiv) were added and the reaction was stirred for 20 hours at 50 ℃. 250mL acetonitrile/water (v/v1:1) was added to the reaction system, and the precipitate was rinsed 2 times with 250mL acetonitrile/water (v/v1: 1). The product was dried under vacuum at room temperature to give 101g of Compound 2a, with 14.5% trityl protected mercaptopropionic acid with PVA attached, Hydrogen Spectroscopy (400MHz, DMSO-d)6) See fig. 1.
(2) Synthesis of Compound 3a
Compound 2a was added to TFA/water/trisisopyrolisane (10vol:1 v)ol:0.6vol) mixed system, and reacting for 2 hours at normal temperature; concentrating to remove TFA, adding MeOH (5vol) and 0.3M sulfuric acid (10vol) respectively, and reacting at 60 ℃ for 3 hours; adding acetonitrile (5vol) to precipitate the product, washing with acetonitrile (2vol), and freeze-drying to obtain product 3a containing 12% of sulfydryl and having hydrogen spectrum (400MHz, D)2O) is shown in FIG. 2.
Example 2
The invention provides a preparation method of high sulfydryl functionalized polyvinyl alcohol, which comprises the following synthetic route:
(1) synthesis of Compound 2b
Acetyl free PVA 1b (50g, MW 30000Da) was added to DMF (850mL), the reaction was raised to 95 ℃ and stirred for one hour until PVA was completely dissolved, then reduced to 50 ℃ and trityl protected mercaptobutanoic acid 4b (0.6g, 1.3equiv), EDCI (0.34g,1.2equiv) and DMAP (60mg,0.4equiv) were added and the reaction was stirred for 20 hours at 50 ℃. 250mL of acetonitrile/water (v/v1:1) was added to the reaction system, and the precipitate was rinsed 2 times with 250mL of acetonitrile/water (v/v1: 1). The product was dried under vacuum at room temperature to give 99g of compound 2a with 20% trityl protected mercaptobutanoic acid attached to PVA.
(2) Synthesis of Compound 3b
Adding the compound 2b into a TFA/water/trisisopyvalene (10vol:1vol:0.6vol) mixed system, and reacting for 2 hours at normal temperature; TFA was removed by concentration, and the product was precipitated by addition of acetonitrile (5vol), washed with acetonitrile (2vol) and lyophilized to give product 3b containing 18% mercapto groups.
Claims (10)
1. A mercapto-functionalized polyvinyl alcohol has a structure shown in formula I:
wherein R ═ H or
q is 1, 2, 3 or 4, and m and n are natural numbers of 1 to 1000.
2. The process for the preparation of mercapto-functionalized polyvinyl alcohol of claim 1, comprising the steps of:
(1) carrying out esterification reaction on polyvinyl alcohol 1 and trityl protected mercapto fatty acid 4 under the catalysis of EDCI and DMAP to obtain a compound 2;
(2) the trityl group of the compound 2 is removed by a TFA/water/trisisopyropyllane system, and the acetyl group is selectively hydrolyzed by a sulfuric acid/methanol system to obtain the sulfhydryl functional polyvinyl alcohol 3.
3. The method of claim 2, wherein in step (1), the polyvinyl alcohol 1 contains or does not contain acetyl, and the solvent is DMF.
4. The method for preparing thiol-functionalized polyvinyl alcohol according to claim 2, wherein in step (1), the polyvinyl alcohol 1 is taken and dissolved in DMF, and then trityl-protected thiol fatty acid 4 is added to react with the catalyst, wherein the ratio of the polyvinyl alcohol 1 to the trityl-protected thiol fatty acid 4 is 1:1 to 1.5.
5. The method according to claim 3, wherein in step (1), EDCI is used in an amount of 1-1.5 times that of trityl-protected mercaptofatty acid 4, and DMAP is used in an amount of 0.2-0.5 times that of trityl-protected mercaptofatty acid 4.
6. The method according to claim 2, wherein in step (1), the trityl-protected mercaptofatty acid 4 is trityl-protected mercaptoacetic acid, propionic acid, butyric acid, or valeric acid.
7. The process for preparing a mercapto-functionalized polyvinyl alcohol according to claim 2, wherein in step (2), the TFA/water/trisisopyro silane system has a volume ratio of 8 to 12: 0.5-2: 0.4-0.8.
8. The method for preparing mercapto-functionalized polyvinyl alcohol according to claim 2, wherein in step (2), the volume ratio of 0.3M sulfuric acid/methanol system is 8-12: 3 to 6.
9. The method for preparing thiol-functionalized polyvinyl alcohol according to claim 2, wherein after the reaction of step (1) and step (2), acetonitrile, water, isopropanol, methanol, ethanol, etc. are added to precipitate the product.
10. Use of the mercapto-functionalized polyvinyl alcohol of claim 1 for mercury removal from water.
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