CN110066354A - A kind of solid macromolecule reducing agent and preparation method thereof - Google Patents
A kind of solid macromolecule reducing agent and preparation method thereof Download PDFInfo
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- CN110066354A CN110066354A CN201910260535.5A CN201910260535A CN110066354A CN 110066354 A CN110066354 A CN 110066354A CN 201910260535 A CN201910260535 A CN 201910260535A CN 110066354 A CN110066354 A CN 110066354A
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 54
- 239000007787 solid Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229920002521 macromolecule Polymers 0.000 title abstract description 4
- 239000011159 matrix material Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000002829 reductive effect Effects 0.000 claims abstract description 10
- 239000004793 Polystyrene Substances 0.000 claims abstract description 8
- 229920002223 polystyrene Polymers 0.000 claims abstract description 8
- 238000007265 chloromethylation reaction Methods 0.000 claims abstract description 6
- 238000005342 ion exchange Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 229920000642 polymer Polymers 0.000 claims description 49
- 239000000047 product Substances 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 33
- 239000012265 solid product Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000012071 phase Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 239000012452 mother liquor Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 13
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 13
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 13
- -1 hydrocarbon radicals Chemical class 0.000 claims description 13
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 230000008961 swelling Effects 0.000 claims description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 230000001603 reducing effect Effects 0.000 claims description 6
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 238000005956 quaternization reaction Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 4
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 4
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 2
- 229940099427 potassium bisulfite Drugs 0.000 claims description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 2
- 235000019252 potassium sulphite Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 239000008346 aqueous phase Substances 0.000 claims 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 150000001298 alcohols Chemical class 0.000 abstract description 3
- 150000001412 amines Chemical class 0.000 abstract description 3
- 150000003384 small molecules Chemical class 0.000 abstract description 3
- 239000002262 Schiff base Substances 0.000 abstract description 2
- 150000004753 Schiff bases Chemical class 0.000 abstract description 2
- 150000002466 imines Chemical class 0.000 abstract description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000011324 bead Substances 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 229920000307 polymer substrate Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910001412 inorganic anion Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 102000004196 processed proteins & peptides Human genes 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 108091034117 Oligonucleotide Proteins 0.000 description 1
- JLCPHMBAVCMARE-UHFFFAOYSA-N [3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[5-(2-amino-6-oxo-1H-purin-9-yl)-3-[[3-[[3-[[3-[[3-[[3-[[5-(2-amino-6-oxo-1H-purin-9-yl)-3-[[5-(2-amino-6-oxo-1H-purin-9-yl)-3-hydroxyoxolan-2-yl]methoxy-hydroxyphosphoryl]oxyoxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxyoxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methyl [5-(6-aminopurin-9-yl)-2-(hydroxymethyl)oxolan-3-yl] hydrogen phosphate Polymers Cc1cn(C2CC(OP(O)(=O)OCC3OC(CC3OP(O)(=O)OCC3OC(CC3O)n3cnc4c3nc(N)[nH]c4=O)n3cnc4c3nc(N)[nH]c4=O)C(COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3CO)n3cnc4c(N)ncnc34)n3ccc(N)nc3=O)n3cnc4c(N)ncnc34)n3ccc(N)nc3=O)n3ccc(N)nc3=O)n3ccc(N)nc3=O)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)n3cc(C)c(=O)[nH]c3=O)n3cc(C)c(=O)[nH]c3=O)n3ccc(N)nc3=O)n3cc(C)c(=O)[nH]c3=O)n3cnc4c3nc(N)[nH]c4=O)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)O2)c(=O)[nH]c1=O JLCPHMBAVCMARE-UHFFFAOYSA-N 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
Classifications
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- 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
- C08F8/42—Introducing metal atoms or metal-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of preparation method of solid macromolecule reducing agent, this method mainly includes the following steps: the preparation and purification of 1, polystyrene backbone matrix: 2, the chloromethylation of polystyrene backbone matrix；3, chloromethylated polystyrene skeletal matrix is quaternized；4, the introducing of reproducibility ion-exchange group.The indexs such as the specific surface area and functional group content of the reducing agent can be regulated and controled.Solid macromolecule reducing agent of the invention can wide participation reduction reaction, such as nitro class and imines (schiff bases) compound be reduced to corresponding amine, aldehyde ketone carbonyls is reduced to corresponding alcohols etc..Compared with traditional small molecule reducing agent, the present invention has many advantages, such as that stable storing, stereoselectivity are good, can be easily separated, is renewable, is expected to be applied to industrialized production.
Description
Technical Field
The invention belongs to the field of high molecular materials, relates to preparation of a solid high molecular reducing agent, and particularly relates to a preparation method of a high molecular solid reducing agent which takes a quaternary ammonium type organic high molecular polymer as a matrix and carries reductive inorganic anions.
Background
The high molecular reagent is a functional high molecular material which is prepared by bonding a small molecular reagent or a small molecular reaction substrate in organic synthesis to a polymer molecular chain through a functionalization reaction and then carrying out an organic synthesis reaction.
The application of the high molecular reagent is traced to the middle of the 30 th of the 20 th century, and the preparation of the ion exchange resin by a polycondensation method is taken as a starting point. Ion exchange resin and electron exchange resin using styrene-divinylbenzene as a matrix were prepared in 1944, but the advantages of polymer loading reaction were not fully realized until 1963 when r.b. merrifield and r.l. letecinge successfully performed solid phase synthesis of peptides on a polymer carrier, and research on polymer reagents was also paid attention to, and various polymer reagents were synthesized successively, and combinatorial chemistry techniques were developed at the end of 80 s, which were effectively applied to the development of new materials and drugs, the synthesis and resolution of chiral compounds, the solid phase synthesis of polypeptides, oligonucleotides and oligosaccharides, the research on organic synthesis reaction mechanism, specific separation, analysis and clinical assay, hydrometallurgy and biomedicine, etc.
Compared with the traditional liquid micromolecule reagent, the macromolecule reagent combines the advantages of both the polymer skeleton and the reactive group, and has the advantages of easy separation, reproducibility, good stability and safety, high reaction specificity and selectivity, environmental friendliness, suitability for continuous and mechanized operation and the like.
Depending on the function, polymeric reagents are generally classified into polymeric redox reagents, polymeric halogenating reagents, polymeric acylating reagents, polymeric alkylating reagents, polymeric nucleophilic reagents, and the like, and can participate in various reactions such as oxidation, reduction, halogenation, acylation, alkylation, azotization, nucleophilicity, electrophilicity, condensation, and the like.
The macromolecular reducing agent is a macromolecular reagent which is mainly prepared by polymerizing a micromolecular reducing agent and still maintains the reduction characteristic. The polymeric reducing agent mainly includes a polymeric organic metal compound, a polymeric sulfonyl hydrazide, a polymeric thiol, and a reducing agent obtained by combining a polymeric complex, an ion exchange resin, a polymeric adsorbent, and the like with a small molecular reducing agent (inorganic or organic agent) according to the type of the reducing agent contained and the manner of combining the polymeric framework with the reducing agent.
The traditional small molecule reducing agent has the following disadvantages: 1. the chemical stability and safety are poor, and the material is flammable, explosive and easy to lose efficacy, so that the storage, transportation and use are difficult; 2. the environment is not friendly, the organic small molecular reducing agent is generally low in boiling point or volatile, has unpleasant odor and high toxicity at normal temperature, and deteriorates the working environment; 3. the post-treatment is difficult, and after part of reducing agents participate in the reduction reaction, oxidation products and main products are mixed, so that the separation is difficult, and more complicated post-treatment steps are required.
In summary, the present invention aims to provide a novel solid polymeric reducing agent and a preparation method thereof, wherein the novel solid polymeric reducing agent is convenient to prepare, high in reactivity and selectivity, stable in safety, easy to separate, and convenient to recover and regenerate.
Disclosure of Invention
Aiming at the problems of the existing small molecular reducing agent, the invention provides a novel solid polymer reducing agent, the reagent takes quaternized styrene-divinylbenzene or styrene-diethylene glycol dimethacrylate copolymer as a substrate, and the substrate carries inorganic anions with reducing action through electrostatic attraction. The reagent has good reaction activity, and can participate in reduction reaction to convert small molecular compounds such as aldehyde, ketone, nitrile, oxime, nitro compounds, imine (Schiff base) compounds and the like into small molecular alcohols and amines.
In order to achieve the above purpose, the preparation method of the solid polymer reducing agent provided by the invention adopts the following specific steps:
1. polymerization reaction:
(1) adding 0.4-1 part by mass of Benzoyl Peroxide (BPO) into a mixed solution of 40-100 parts by mass of styrene (St) and 1-60 parts by mass of a cross-linking agent, stirring at normal temperature to completely dissolve the benzoyl peroxide, adding 0-250 parts by mass of a pore-forming agent, stirring and mixing uniformly to prepare an oil phase.
(2) Adding 2.5-9 parts by mass of polyvinyl alcohol 1788 into 1000 parts by mass of water of 300-.
(3) Slowly adding the oil phase into the water phase, standing for 10min, stirring to adjust oil drop to a proper particle size range, heating to 80-90 deg.C, reacting for 8-14h, stopping reaction, and cooling to 40-50 deg.C.
(4) Filtering out reaction mother liquor, washing the solid product with 50 ℃ hot water and petroleum ether in sequence until no oil mark is left on the washing liquid point plate, drying the solid product at 50-60 ℃ and then sieving to the required granularity specification to obtain the polymer matrix with the polystyrene skeleton.
2. Chloromethylation reaction:
(1) 100 parts by mass of polymer matrix, 500-1000 parts by mass of 1, 2-dichloroethane and 50-200 parts by mass of chloromethyl ether are mixed and stirred for swelling for 1-1.5h at 20-35 ℃.
(2) Heating to 40-45 ℃, adding 40-160 parts by mass of anhydrous zinc chloride into the reaction system for 2-3 times under stirring, wherein the interval is 20-30min each time, gradually heating to 50-60 ℃ in the period, keeping the temperature for reaction for 8-18h, and stopping the reaction.
(3) Filtering out reaction mother liquor, washing the solid product with 1, 2-dichloroethane, ethanol and water for 3 times respectively, and draining free water to obtain the chloromethylated polymer matrix.
3. Quaternization reaction:
(1) swelling the chloromethylated polymer matrix obtained in the step (2) for 2h by using 400-800 parts by mass of quaternizing agent under stirring at 25-30 ℃.
(2) Heating to 40-45 ℃, keeping the temperature for reaction for 15-20h, and stopping the reaction.
(3) The reaction mother liquor is filtered off, the solid product is washed with water until the effluent pH is 7-8, and the free water is drained to give the quaternized polymer matrix.
4. Ion exchange reaction:
(1) 100 parts by mass of the quaternized polymer matrix are packed into a column by a wet method, 1200 parts by mass of 2400 parts by mass of sodium hydroxide aqueous solution (the mass percentage concentration is 3-5%) are used for leaching the matrix, and the flow rate is 0.3-0.7 BV/h.
(2) And (4) leaching the matrix by pure water until the pH of the effluent is 7-8, discharging the effluent into a reactor, and pumping free water.
(3) Adding 200-400 parts by mass of pure water into a reactor, soaking the substrate, adding 15-25 parts by mass of reducing inorganic salt, stirring and dissolving at 25-30 ℃, and then carrying out heat preservation reaction for 16-20 h.
(4) And (3) filtering out liquid after the reaction is finished, washing the solid product with pure water until the pH of the effluent liquid is 7, washing the solid product with ethanol for 4 times, wherein the dosage of the product is 2-3 times of the mass of the product each time, washing the product for 15-30min each time, draining the solvent after washing, drying the product at room temperature, and drying the product at 40-45 ℃ until the volatile component is less than 2% to obtain the finished product of the solid macromolecular reducing agent.
The crosslinking agent in the step 1 is one of 75-85% of Divinylbenzene (DVB) and diethylene glycol dimethacrylate (DEGDMA).
The pore-forming agent in the step 1 is alkane or aromatic hydrocarbon such as toluene, ethylbenzene, xylene, n-heptane, 200# gasoline and the like, or alcohol or ester such as cyclohexanol, isoamyl alcohol, n-octanol, dodecanol, butyl acetate and the like, or a combination of one of the former and one of the latter, wherein the former accounts for 33-67% of the total mass of the pore-forming agent.
The quaternizing agent in the step 3 is one of trimethylamine, triethylamine, tripropylamine, N-dimethylethylamine, N-diisopropylethylamine, N-dimethylethanolamine, N-dimethylpropanolamine, N-dimethylisopropanolamine, triethanolamine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine and 2-ethylpyridine.
The reducing inorganic salt in the step 4 is one of sodium bisulfite, potassium bisulfite, sodium sulfite, potassium sulfite, sodium cyanoborohydride and potassium cyanoborohydride.
The basic indexes of the novel solid polymer reducing agent obtained according to the preparation steps are as follows:
the appearance is white to light yellow flaky or filiform or granular substance, and the specific surface area is 0-1500m2Per g, the radical content is 0.1-5.0 mmol/g.
The primary application results of the obtained novel solid macromolecular reducing agent are as follows:
the solid macromolecular reducing agent which is prepared by taking a styrene-bis (ethylene glycol) dimethacrylate copolymer aminated by N, N-dimethylethanolamine as a substrate and carries cyanoborohydride radicals, the granularity is 0.3-0.6mm, the cyanoborohydride radical content is 0.49mmol/g, nitrobenzene is reduced in the presence of ammonium sulfate in tetrahydrofuran to generate aniline, and the yield is 97.4%.
The solid macromolecular reducing agent which is prepared by taking a styrene-divinylbenzene copolymer aminated by triethylamine as a substrate and carries the hydrosulfite radical has the granularity of 0.04-0.08mm and the hydrosulfite radical content of 1.76mmol/g, and the cyclohexanone is reduced in tetrahydrofuran to generate the cyclohexanol with the yield of 98.3 percent.
The solid macromolecular reducing agent which is prepared by taking trimethylamine aminated styrene-divinylbenzene copolymer as a substrate and carries cyanoborohydride groups, the granularity of the solid macromolecular reducing agent is 0.09-0.15mm, the cyanoborohydride group content is 1.25mmol/g, tetrahydrofuran is filled into a column, benzaldehyde passes through the column to carry out reduction reaction, and benzyl alcohol is generated, and the yield is 99.8%.
The beneficial effects of the technical process adopted by the invention can be illustrated by the following aspects:
1. the solid polymer reducing agent provided by the invention is simple to prepare, the molecular weight is improved through polymerization on the premise of keeping the activity of the reagent, the volatility and the sensitivity of the reagent are reduced, the physical and chemical stability of the reagent is obviously improved, and the working environment and the safety of use, storage and transportation are improved.
2. The solid polymer reducing agent provided by the invention can realize the so-called infinite dilution and the 'ortho effect' which are difficult to achieve in small molecule reaction due to the separation and fixation of the polymer framework, avoid or reduce side reaction, improve the specificity of the reaction, and simultaneously realize the so-called 'template reaction' by utilizing the stereo effect of the polymer framework, thereby having a certain effect on improving the selectivity of the reaction.
3. The side reaction and reverse reaction of the solid polymer reducing agent participating in organic or polymer synthesis reaction are greatly reduced, so that proper excess reaction substrate can be added in the reaction to improve the yield, the excess reactant can be recycled, and in the use mode, the reagent can be arranged in a reaction column for continuous cycle operation, thereby being beneficial to the automation of the synthesis reaction.
4. The solid polymer reducing agent provided by the invention can be separated only by simple filtration or centrifugation after a homogeneous reaction is converted into a heterogeneous reaction due to the insolubility of a polymer skeleton and reacts with a low molecular compound, so that the separation and purification process of a product is simplified, the recovery and the regeneration are convenient, the cost can be effectively reduced, the pollution is reduced, and the solid polymer reducing agent is suitable for industrial production.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to only the following examples.
Example 1
(1) Polymerization reaction:
i. to a mixture of 93 parts by mass of styrene (St) and 7 parts by mass of diethylene glycol dimethacrylate (DEGDMA), 1 part by mass of Benzoyl Peroxide (BPO) was added, and the mixture was stirred at room temperature to be completely dissolved to prepare an oil phase.
ii, adding 6 parts by mass of polyvinyl alcohol 1788 into 600 parts by mass of water, and stirring for 3 hours at 60 ℃ to completely dissolve the polyvinyl alcohol to prepare a water phase.
And iii, slowly adding the oil phase into the water phase, standing for 10min, stirring to adjust the oil drop to a proper particle size range, heating to 85 ℃, reacting for 14h, stopping the reaction, and cooling to 50 ℃.
And iv, filtering out reaction mother liquor, washing with hot water at 50 ℃ until a washing liquid is clear, converting into an ethanol phase, draining the solvent, airing at room temperature, drying a solid product at 60 ℃ until the volatile content is less than 2%, and screening the product with the particle size of 0.3-0.6mm to obtain the colorless pearl-shaped semitransparent polymer matrix with the polystyrene skeleton.
(2) Chloromethylation reaction:
i. 100 parts by mass of the bead polymer matrix were mixed with 500 parts by mass of 1, 2-dichloroethane and 50 parts by mass of chloromethyl ether and swollen with stirring at 25 ℃ for 1 hour.
And ii, heating to 40 ℃, adding 40 parts by mass of anhydrous zinc chloride into the reaction system for 2 times under stirring, gradually heating to 60 ℃ every time at intervals of 20min, keeping the temperature for reaction for 8 hours, and stopping the reaction.
Filtering the reaction mother liquor, washing the solid product with 1, 2-dichloroethane, ethanol and water sequentially for 3 times, and draining the free water to obtain white beaded translucent chloromethylated polymer matrix.
(3) Quaternization reaction:
swelling the chloromethylated polymer matrix obtained in the step (2) with 400 parts by mass of N, N-dimethylethanolamine for 2h at 25 ℃ under stirring.
And ii, raising the temperature to 40 ℃, preserving the temperature and reacting for 15 hours, and stopping the reaction.
The reaction mother liquor was filtered off, the solid product was washed with water until the effluent pH was 7, and the free water was drained to give a white beaded translucent quaternized polymer matrix.
(4) Ion exchange reaction:
i. 100 parts by mass of beaded quaternized polymer substrate were wet-pillared and the substrate was rinsed with 1200 parts by mass of aqueous sodium hydroxide solution (3% by mass) at a flow rate of 0.7 BV/h.
Rinsing the matrix with pure water until the pH of the effluent is 7, discharging the effluent into a reactor, and pumping free water.
And iii, adding 300 parts by mass of pure water into the reactor, soaking the substrate, adding 15 parts by mass of sodium cyanoborohydride, stirring at 25 ℃ to dissolve, and then carrying out heat preservation reaction for 16 hours.
And iv, filtering out liquid after the reaction is finished, washing the solid product with pure water until the pH of an effluent liquid is 7, washing the solid product with ethanol for 4 times, wherein the dosage of the product is 3 times of the mass of the product each time, washing the product for 30min each time, draining the solvent after washing, drying the product at room temperature, and drying the product at 40 ℃ until the volatile component is less than 2% to obtain a finished product 1 of the solid macromolecular reducing agent.
(5) The solid polymeric reducing agent obtained in example 1 is white semitransparent beads with the particle size of 0.3-0.6mm, the cyanoborohydride content of 0.49mmol/g, and the swelling degree in N, N-dimethylformamide of 6.2 ml/g.
Example 2
(1) Polymerization reaction:
i. adding 1 part by mass of Benzoyl Peroxide (BPO) into a mixed solution of 50 parts by mass of styrene (St) and 50 parts by mass of 80% Divinylbenzene (DVB), stirring at normal temperature to completely dissolve the benzoyl peroxide, adding 133 parts by mass of toluene and 67 parts by mass of dodecanol, stirring to completely dissolve the toluene and the dodecanol, and uniformly mixing to prepare an oil phase.
And ii, adding 9 parts by mass of polyvinyl alcohol 1788 into 900 parts by mass of water, and stirring for 2-4 hours at 60 ℃ to completely dissolve the polyvinyl alcohol to prepare a water phase.
And iii, slowly adding the oil phase into the water phase, standing for 10min, stirring to adjust the oil drop to a proper particle size range, heating to 88 ℃, reacting for 12h, stopping the reaction, and cooling to 50 ℃.
And iv, filtering out the reaction mother liquor, washing the solid product with 50 ℃ hot water and petroleum ether in sequence until no oil mark is left on the plate at the point of the eluate, draining the solvent, drying the solid product at room temperature, and screening the solid product with the granularity of 0.04-0.08mm to obtain a white bead-shaped opaque polystyrene matrix.
(2) Chloromethylation reaction:
i. 100 parts by mass of the bead polymer matrix were mixed with 600 parts by mass of 1, 2-dichloroethane and 100 parts by mass of chloromethyl ether and swollen with stirring at 25 ℃ for 1 hour.
And ii, heating to 40 ℃, adding 80 parts by mass of anhydrous zinc chloride into the reaction system for 3 times under stirring, gradually heating to 60 ℃ every time at intervals of 20min, keeping the temperature for reaction for 10 hours, and stopping the reaction.
And iii, filtering out reaction mother liquor, washing the solid product by sequentially using 1, 2-dichloroethane, ethanol and pure water for 3 times respectively, and draining free water to obtain a light yellow pearl-shaped opaque chloromethylated polymer matrix.
(3) Quaternization reaction:
the chloromethylated polymer matrix obtained in the step (2) was swelled with 600 parts by mass of triethylamine under stirring at i.25 ℃ for 2 h.
And ii, raising the temperature to 45 ℃, preserving the temperature and reacting for 20 hours, and stopping the reaction.
The reaction mother liquor was filtered off, the solid product was washed with water to an effluent pH of 8, and the free water was drained to give a pale yellow beaded translucent quaternized polymer matrix.
(4) Ion exchange reaction:
i. 100 parts by mass of beaded quaternary ammonium polymer substrate were wet-pillared and the substrate was rinsed with 2400 parts by mass of aqueous sodium hydroxide (4% by mass) at a flow rate of 0.7 BV/h.
Rinsing the matrix with pure water until the pH of the effluent is 7, discharging the effluent into a reactor, and pumping free water.
And iii, adding 400 parts by mass of pure water into the reactor, soaking the substrate, adding 25 parts by mass of sodium bisulfite, stirring at 30 ℃ to dissolve, and then carrying out heat preservation reaction for 20 hours.
And iv, filtering out liquid after the reaction is finished, washing the solid product with pure water until the pH of an effluent liquid is 7, washing the solid product with ethanol for 4 times, wherein the dosage of the product is 3 times of the mass of the product each time, washing the product for 20min each time, draining the solvent after washing, drying the product at room temperature, and drying the product at 40 ℃ until the volatile component is less than 2% to obtain a finished product 2 of the solid macromolecular reducing agent.
(5) The solid polymeric reducing agent obtained in example 2 was light yellow opaque beads in appearance, having a particle size of 0.04 to 0.08mm, a hydrogen sulfite content of 1.76mmol/g, a swelling degree in N, N-dimethylformamide of 7.9ml/g, and a specific surface area of 370m2/g。
Example 3
(1) Polymerization reaction:
i. 0.7 part by mass of Benzoyl Peroxide (BPO) was added to a mixture of 97 parts by mass of styrene (St) and 3 parts by mass of 80% Divinylbenzene (DVB), and the mixture was stirred at room temperature to be completely dissolved to prepare an oil phase.
ii, adding 8 parts by mass of polyvinyl alcohol 1788 into 800 parts by mass of water, stirring at 60 ℃ for 3 hours to completely dissolve the polyvinyl alcohol, and preparing a water phase.
And iii, slowly adding the oil phase into the water phase, standing for 10min, stirring to adjust the oil drop to a proper particle size range, heating to 85 ℃, reacting for 12h, stopping the reaction, and cooling to 50 ℃.
And iv, filtering out reaction mother liquor, washing with hot water at 50 ℃ until a washing liquid is clear, converting into an ethanol phase, draining the solvent, airing at room temperature, drying a solid product at 60 ℃, and screening to obtain a product with the granularity of 0.09-0.15mm to obtain the colorless pearl-shaped semitransparent polystyrene matrix.
(2) Chloromethylation reaction:
i. 100 parts by mass of the bead polymer matrix were mixed with 650 parts by mass of 1, 2-dichloroethane and 50 parts by mass of chloromethyl ether and swollen with stirring at 25 ℃ for 1.5 h.
And ii, heating to 45 ℃, adding 60 parts by mass of anhydrous zinc chloride into the reaction system for 3 times under stirring, gradually heating to 60 ℃ every time at intervals of 30min, keeping the temperature for reaction for 11 hours, and stopping the reaction.
And iii, filtering out the reaction mother liquor, washing the solid product by sequentially using 1, 2-dichloroethane, ethanol and pure water for 3 times respectively, and draining free water to obtain a light yellow bead-shaped semitransparent chloromethylated polymer matrix.
(3) Quaternization reaction:
the chloromethylated polymer matrix obtained in the above step (2) was swelled with 600 parts by mass of trimethylamine under stirring at i.25 ℃ for 2 h.
And ii, raising the temperature to 40 ℃, preserving the temperature and reacting for 20 hours, and stopping the reaction.
The reaction mother liquor is filtered off, the solid product is washed with water until the effluent pH is 8, and the free water is drained to give a translucent quaternized polymer matrix in the form of pale yellow beads.
(4) Ion exchange reaction:
i. 100 parts by mass of beaded quaternary ammonium polymer substrate were wet-packed in a column, and the substrate was rinsed with 2000 parts by mass of aqueous sodium hydroxide (4% by mass) at a flow rate of 0.5 BV/h.
Rinsing the matrix with pure water until the pH of the effluent is 7, discharging the effluent into a reactor, and pumping free water.
And iii, adding 300 parts by mass of pure water into the reactor, soaking the substrate, adding 20 parts by mass of potassium cyanoborohydride, stirring at 25 ℃ to dissolve, and then carrying out heat preservation reaction for 18 hours.
And iv, filtering out liquid after the reaction is finished, washing the solid product with pure water until the pH of an effluent liquid is 7, washing the solid product with ethanol for 4 times, wherein the dosage of the product is 2 times of the mass of the product each time, washing the product for 30min each time, draining the solvent after washing, drying the product at room temperature, and drying the product at 40 ℃ until the volatile component is less than 2% to obtain a finished product 3 of the solid macromolecular reducing agent.
(5) The solid polymeric reducing agent obtained in example 3 is light yellow semitransparent beads with the particle size of 0.09-0.15mm, the cyanoborohydride content of 1.25mmol/g and the swelling degree in N, N-dimethylformamide of 6.8 ml/g.
The primary application results of the obtained novel solid macromolecular reducing agent are as follows:
the finished product 1 of the solid polymeric reducing agent obtained in example 1 is subjected to nitrobenzene reduction in the presence of ammonium sulfate in tetrahydrofuran to produce aniline with a yield of 97.4%.
The finished product 2 of the solid polymeric reducing agent obtained in example 2 was used to reduce cyclohexanone in tetrahydrofuran to produce cyclohexanol with a yield of 98.3%.
The solid polymer reducing agent product 3 obtained in example 3 was loaded onto a column with tetrahydrofuran, and benzaldehyde was passed through the column to cause a reduction reaction, thereby producing benzyl alcohol with a yield of 99.8%.
The novel solid polymer reducing agent prepared by the invention can better participate in various reduction reactions to convert aldehyde ketone and nitro micromolecule compounds into corresponding micromolecule alcohols and amines, has the reaction activity not lower than that of the traditional micromolecule reducing agent, is convenient to store and easy to separate and regenerate, can improve the yield through column type dynamic reaction, and is expected to be applied to industrial production.
Claims (7)
1. A solid polymer reducing agent is white to light yellow flaky, filamentous or granular substance with specific surface area of 0-1500m2The content of groups is 0.1-5.0mmol/g, and the structure is quaternary ammonium type styrene-divinylbenzene copolymer or styrene-diethylene glycol dimethacrylate copolymer carrying reductive anions.
2. The structural formula of the solid polymeric reducing agent according to claim 1 is shown as follows:
wherein,is a polymer matrix, R are identical or different hydrocarbon radicals, X-Is a reducing anion.
3. The method for preparing a solid polymeric reducing agent according to claim 1, comprising the steps of:
(1) polymerization reaction:
i. adding 0.4-1 part by mass of Benzoyl Peroxide (BPO) into a mixed solution of 40-100 parts by mass of styrene (St) and 1-60 parts by mass of a cross-linking agent, stirring at normal temperature to completely dissolve the benzoyl peroxide, adding 0-250 parts by mass of a pore-forming agent, stirring and mixing uniformly to prepare an oil phase.
ii, adding 2.5-9 parts by mass of polyvinyl alcohol 1788 into 300-1000 parts by mass of water, and stirring for 2-4h at 50-60 ℃ to completely dissolve the polyvinyl alcohol to prepare an aqueous phase.
And iii, slowly adding the oil phase into the water phase, standing for 10min, stirring to adjust the oil drop to a proper particle size range, heating to 80-90 ℃, reacting for 8-14h, stopping the reaction, and cooling to 40-50 ℃.
And iv, filtering out the reaction mother liquor, washing the solid product with hot water at 50 ℃ and petroleum ether in sequence until no oil mark is left on the plate at the washing liquid point, drying the solid product at 50-60 ℃, and screening to the required particle size specification to obtain the polymer matrix with the polystyrene skeleton.
(2) Chloromethylation reaction:
i. 100 parts by mass of polymer matrix, 500-1000 parts by mass of 1, 2-dichloroethane and 50-200 parts by mass of chloromethyl ether are mixed and stirred for swelling for 1-1.5h at 20-35 ℃.
And ii, heating to 40-45 ℃, adding 40-160 parts by mass of anhydrous zinc chloride into the reaction system for 2-3 times under stirring, wherein the interval is 20-30min each time, gradually heating to 50-60 ℃ in the period, keeping the temperature for reacting for 8-18h, and stopping the reaction.
And iii, filtering out the reaction mother liquor, washing the solid product with 1, 2-dichloroethane, ethanol and water for 3 times respectively, and draining free water to obtain the chloromethylated polymer matrix.
(3) Quaternization reaction:
swelling the chloromethylated polymer matrix obtained in the step (2) for 2h by using 400-800 parts by mass of quaternizing agent under stirring at the temperature of 25-30 ℃.
And ii, heating to 40-45 ℃, keeping the temperature for reaction for 15-20h, and stopping the reaction.
Filtering the reaction mother liquor, washing the solid product with water until the effluent pH is 7-8, and draining the free water to obtain the quaternized polymer matrix.
(4) Ion exchange reaction:
i. 100 parts by mass of the quaternized polymer matrix are packed into a column by a wet method, 1200 parts by mass of 2400 parts by mass of sodium hydroxide aqueous solution (the mass percentage concentration is 3-5%) are used for leaching the matrix, and the flow rate is 0.3-0.7 BV/h.
And ii, rinsing the matrix with pure water until the pH of the effluent is 7-8, discharging the effluent into a reactor, and pumping free water.
And iii, adding 200-400 parts by mass of pure water into the reactor, soaking the substrate, adding 15-25 parts by mass of reducing inorganic salt, stirring and dissolving at 25-30 ℃, and then carrying out heat preservation reaction for 16-20 h.
And iv, filtering out liquid after the reaction is finished, washing the solid product with pure water until the pH of an effluent liquid is 7, washing the solid product with ethanol for 4 times, wherein the dosage of the product is 2-3 times of the mass of the product each time, washing the product for 15-30min each time, draining the solvent after washing, drying the product at room temperature, and drying the product at 40-45 ℃ until the volatile component is less than 2% to obtain a finished product of the solid macromolecular reducing agent.
4. The method for preparing a solid polymeric reducing agent according to claim 3, wherein the crosslinking agent in the step (1) is one of 75-85% of Divinylbenzene (DVB) and diethylene glycol dimethacrylate (DEGDMA).
5. The method for preparing a solid polymeric reducing agent according to claim 3, wherein the pore-forming agent in step (1) is an alkane or aromatic hydrocarbon such as toluene, ethylbenzene, xylene, n-heptane, 200# gasoline, or an alcohol or ester such as cyclohexanol, isoamyl alcohol, n-octanol, dodecanol, butyl acetate, or a combination of one of the former and one of the latter, wherein the former accounts for 33-67% of the total mass of the pore-forming agent.
6. The method according to claim 3, wherein the quaternizing agent in the step (3) is one of trimethylamine, triethylamine, tripropylamine, N-dimethylethylamine, N-diisopropylethylamine, N-dimethylethanolamine, N-dimethylpropanolamine, N-dimethylisopropanolamine, triethanolamine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, and 2-ethylpyridine.
7. The method for preparing a solid polymeric reducing agent according to claim 3, wherein the reducing inorganic salt in the step (4) is one of sodium bisulfite, potassium bisulfite, sodium sulfite, potassium sulfite, sodium cyanoborohydride, and potassium cyanoborohydride.
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| P. HODGE等: "硼氢阴离子交换树脂的制备及其对羰基、酰氯化合物的还原", 《有机化学》 * |
| 覃彩芹等: "离子交换树脂支载的硼氢离子还原剂", 《咸宁师专学报》 * |
| 陈家威等: "聚合物硼氢阴离子还原剂的制备及其对酯的还原研究", 《应用化学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6944143B1 (en) * | 2021-03-18 | 2021-10-06 | 光夫 木村 | Method for producing reducing agent and method for producing aqueous reducing hydrogen solution |
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