CN105037796A - Long-acting zinc-based heat stabilizer having antibacterial performance, synthetic method and compound - Google Patents
Long-acting zinc-based heat stabilizer having antibacterial performance, synthetic method and compound Download PDFInfo
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- CN105037796A CN105037796A CN201510492646.0A CN201510492646A CN105037796A CN 105037796 A CN105037796 A CN 105037796A CN 201510492646 A CN201510492646 A CN 201510492646A CN 105037796 A CN105037796 A CN 105037796A
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- stabilizer
- zinc
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- heat stabilizer
- pvc
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- 239000011701 zinc Substances 0.000 title claims abstract description 45
- 239000012760 heat stabilizer Substances 0.000 title claims abstract description 27
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 20
- 238000010189 synthetic method Methods 0.000 title claims abstract description 7
- 230000000844 anti-bacterial effect Effects 0.000 title abstract description 10
- 150000001875 compounds Chemical class 0.000 title abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 239000000126 substance Substances 0.000 claims abstract description 11
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 8
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000344 soap Substances 0.000 claims abstract description 6
- 239000003381 stabilizer Substances 0.000 claims description 43
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 230000000845 anti-microbial effect Effects 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 11
- 239000004698 Polyethylene Substances 0.000 claims description 10
- -1 polyethylene Polymers 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 239000001993 wax Substances 0.000 claims description 10
- 239000012188 paraffin wax Substances 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 239000004605 External Lubricant Substances 0.000 claims description 5
- 239000004610 Internal Lubricant Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 5
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 claims description 3
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 claims description 2
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- HRSADIZPZPRZEI-UHFFFAOYSA-L zinc;diacetate;hydrate Chemical compound O.[Zn+2].CC([O-])=O.CC([O-])=O HRSADIZPZPRZEI-UHFFFAOYSA-L 0.000 claims description 2
- WBKFWQBXFREOFH-UHFFFAOYSA-N dichloromethane;ethyl acetate Chemical compound ClCCl.CCOC(C)=O WBKFWQBXFREOFH-UHFFFAOYSA-N 0.000 claims 1
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 60
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 57
- 238000012360 testing method Methods 0.000 abstract description 30
- 241000191967 Staphylococcus aureus Species 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 5
- 239000002262 Schiff base Substances 0.000 abstract description 4
- 150000004753 Schiff bases Chemical class 0.000 abstract description 4
- 239000000314 lubricant Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000032683 aging Effects 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000004246 zinc acetate Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 30
- 239000003017 thermal stabilizer Substances 0.000 description 27
- 239000011347 resin Substances 0.000 description 20
- 229920005989 resin Polymers 0.000 description 20
- 239000002585 base Substances 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 15
- 241000894006 Bacteria Species 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 230000006378 damage Effects 0.000 description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000000968 intestinal effect Effects 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000006084 composite stabilizer Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940023064 escherichia coli Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011158 quantitative evaluation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to a long-acting zinc-based heat stabilizer having an antibacterial performance, a synthetic method and a compound. The heat stabilizer is a zinc-containing product formed by synthesizing Schiff base N1, N3-bi(salicylaldehyde) diethylene triamine (H2L) that is used as a ligand and zinc acetate dehydrate, and a chemical composition of the heat stabilizer is Zn3(HL)2(CH3COO)4. The heat stabilizer can be used as a main heat stabilizer to inhibit the heat aging of polyvinyl chloride (PVC); 5 to 10 parts of the heat stabilizer, 0 to 15 parts of stearate soap, 1 to 3 parts of auxiliary heat stabilizer, 5 to 7 parts of inner lubricating agent and 0 to 5 parts of outer lubricating agent can be used for preparing a heat stabilizer compound which is used for processing PVC. A test result shows that a PVC test piece with the heat stabilizer compound can inhibit a zinc burning phenomenon and also can inhibit colibacillus and staphylococcus aureus. The zinc-based heat stabilizer and a compound thereof are simple in production process, low in cost, small in addition amount, safe and environment-friendly.
Description
Technical field
The invention belongs to polyvinyl chloride (PVC) thermo-stabilizer and antiseptic-germicide technical field, be specifically related to a kind of long-acting zinc-base thermo-stabilizer, synthetic method and the mixture thereof with anti-microbial property.
Background technology
The advantages such as polyvinyl chloride (PVC) is one of five large general-purpose plastics, and have intensity high, corrosion-resistant, electrical insulating property is good, difficult combustion, in addition ripe production technique, PVC is widely used in the every field of industrial or agricultural.But PVC belongs to thermo-sensitivity plastics, at far below the temperature of its processing request, namely thermal destruction occurs, cause its mechanical property and chemical property to be deteriorated, for overcoming this defect, way comparatively general at present adds thermo-stabilizer in the course of processing.
In many PVC heat stabilizer, Ca-Zn composite heat stabilizer is (as calcium stearate (CaSt
2)/Zinic stearas (ZnSt
2) compound system) be commercially applied because of its nontoxic, cheap characteristic and feasible stabilising effect, but along with the increase containing zinc component in composite thermal stabilizer, PVC sample is easily sharply degraded when high temperature (180 ° of C) blackening (industry is called " zinc burning "), and this defect significantly limit the application of Ca-Zn composite heat stabilizer.Therefore postpone zinc and burn one of Research Emphasis becoming Ca-Zn composite heat stabilizer of phenomenon.And along with the raising of health perception, the requirement of people to PVC product anti-microbial property is also more and more higher, but the shortcoming such as antiseptic-germicide ubiquity heavy metal contamination on the market, price are higher, poor compatibility.
Suppressing PVC product thermal destruction for reaching, improving the object of its antibacterial ability.People can add thermo-stabilizer and antiseptic-germicide usually in the PVC course of processing.There are some researches show, nickel salt and the cobalt salt of Schiff's base participation coordination also show good thermostable effect (SabaaMW, MohamedRR, OrabyEH.Vanillin – Schiff ' sbasesasorganicthermalstabilizersandco-stabilizersforrig idpoly (vinylchloride) [J] .Europeanpolymerjournal, 2009,45 (11): 3072-3080).But because nickel salt and cobalt salt be not at calcium zinc heat stabilizer category.And except stainless steel uses nickel, the nickel element in toy material is made strict restriction by European Union REACH (2014/84/EU) instruction.In addition, the price of cobalt element is apparently higher than calcium and zinc element, so the thermo-stabilizer containing cobalt does not have advantage in cost performance.Therefore, adopt Schiff alkali salt to prepare calcium base or zinc-base thermo-stabilizer and remain the field being worth attempting; Recently, we adopt salicylidene Tutofusin tris to be that part has synthesized a kind of zinc salt thermo-stabilizer (ChenG, GuL, YaoY.Anovelzinc-containingadditiveforthelong-termthermal stabilizationofpoly (vinylchloride) [J] .PolymerDegradationandStability, 2014,107:113-119).This thermo-stabilizer shows excellent long-acting thermostable effect, when adding 3 parts, can extend zinc and burn the time to more than 140min.But this zinc salt causes the initial stage color of PVC test piece darker.In addition, although be that some transition metal complexes of part are proved to be and have biological activity that is antiviral, bacteria growing inhibiting with Schiff's base, as far as we know, these title complexs are not yet antibacterial for PVC product.
Because Schiff's base and title complex thereof are generally yellow, as PVC sample usually can be made during thermo-stabilizer to some extent to develop the color, and the initial stage whiteness after sample processing is one of standard of industry member evaluation PVC heat stabilizer effect.Therefore long-acting thermostable effect can be had concurrently and initial stage whiteness judges that can Schiff base zinc title complex under some use conditions as the basic demand of PVC heat stabilizer.Meanwhile, if namely the Schiff base zinc title complex of synthesis itself has antibacterial ability, then can reduce the addition of antiseptic-germicide, reduce the cost of composite thermal stabilizer, simplify production technique.Compare the Schiff's base-zn cpds of our early-stage Study, the invention provides a kind of zinc-base thermo-stabilizer with good initial stage stain resistance.This thermo-stabilizer has good long-acting ageing resistance compared with Zinic stearas, and this thermo-stabilizer has anti-microbial property concurrently.
Summary of the invention
For solving prior art Problems existing, a kind of zinc-base thermo-stabilizer with anti-microbial property provided by the invention and preparation method thereof and mixture, this zinc-base thermo-stabilizer has good initial stage stain resistance, has anti-microbial property concurrently.
The present invention adopts following technical scheme:
The long-acting zinc-base thermo-stabilizer that the present invention has anti-microbial property adopts the Schiff's base N shown in chemical formula-I
1, N
3(code name is H to-bis-(salicylic aldehyde) contracting diethylenetriamine
2l) one as part and Zinc diacetate dihydrate synthesis contains zinc product, and its chemical constitution is Zn
3(HL)
2(CH
3cOO)
4,
Chemical formula-I:N
1, N
3the chemical formula of-bis-(salicylic aldehyde) contracting diethylenetriamine.
Above-mentioned Zn
3(HL)
2(CH
3cOO)
4synthetic method (see figure 1), comprise the following steps:
Step 1. synthesizes N
1, N
3(code name is H to-bis-(salicylic aldehyde) contracting diethylenetriamine
2l)
Get in the 25ml methylene dichloride that 2.06g diethylenetriamine is dissolved in constant pressure funnel, at room temperature it is instilled the dichloromethane solution (4.88g salicylic aldehyde is dissolved in 50ml methylene dichloride) of 77.5g salicylic aldehyde with the speed of 50ml/h, keep room temperature reaction 2-3h afterwards, obtain yellow solution.Suction filtration at 313K temperature, except desolventizing and unreacted raw material, after product is placed in the refrigerator and cooled but 2h of 280K temperature, obtain yellow solid H
2l.
About H
2the characterization result of L: high resolution mass spectrum analysis adopts positive ion mode, finds unique strong fignal center at 312.1705m/z place, consistent with theory expectation.H
2the hydrogen nuclear magnetic resonance spectrum of L is:
1hNMR: δ 13.56 (s, 2H), 8.50 (s, 2H), 7.40 – 7.23 (m, 4H), 6.83 (d, J=7.6Hz, 4H), 3.64 (s, 4H), 2.84 (s, 4H); H
2the infrared spectra FTIR:1615cm of L
-1(C=N), 3258cm
-1(N-H), 3339cm
-1(O-H) (with reference to Fig. 2, Fig. 4).
Step 2: synthesis Zn
3(HL)
2(CH
3cOO)
4
Get 3.11g(0.01mol) H
2l is dissolved in 50ml ethyl acetate, adds 2.19 ~ 3.29g(0.01 ~ 0.015mol) two acetate hydrate zinc, under 318K temperature, agitation condition, react 2h, suction filtration be separated obtain crude product; Then use 20ml ethyl acetate (or methylene dichloride), 20ml water, 20ml ethyl acetate (or methylene dichloride) to amount to washing three times respectively, under 318K temperature condition, vacuum-drying 12h obtains light-yellow precipitate thing, i.e. Zn
3(HL)
2(CH
3cOO)
4.
Zn
3(HL)
2(CH
3cOO)
4hydrogen nuclear magnetic resonance spectrum:
1hNMR: δ 8.36 (s, 2H), 7.27 – 7.04 (m, 4H), 6.63 – 6.34 (m, 4H), 3.64 (s, 4H), 2.83 (s, 4H), 1.83 (s, 6H); FTIR (KBr): 1615cm
-1(C=N), 3229cm
-1(N-H), 1412cm
-1, 1597cm
-1(C=O); Ultimate analysis and ICP:C%50.22, N%7.92, H%4.96Zn%18.5 ~ 19.5, theoretical value C%50.18, N%7.98, H%4.98Zn%18.63 (with reference to Fig. 3, Fig. 4).
The N that step 1 obtains
1, N
3chemical formula-the I of-bis-(salicylic aldehyde) contracting diethylenetriamine is as follows,
。
In step 1, described methylene dichloride can substitute with ethyl acetate or ethanol etc.
Heat stabilizer for PVC mixture (or claiming composite thermal stabilizer) comprising: chemical constitution is Zn
3(HL)
2(CH
3cOO)
4zinc-base thermo-stabilizer 5 ~ 10 parts, stearate soap 0 ~ 15 part, auxiliary heat stabilizer 1 ~ 3 part, internal lubricant 5 ~ 7 parts, external lubricant 0 ~ 5 part.This mixture directly can be used as the thermally-stabilised and anti-microbial property that thermo-stabilizer improves polyvinyl chloride.
The preparation technology of above-mentioned heat stabilizer for PVC mixture is: by Zn
3(HL)
2(CH
3cOO)
45 ~ 10 parts, stearate soap 0 ~ 15 part, auxiliary heat stabilizer 1 ~ 3 part, internal lubricant 5 ~ 7 parts, external lubricant 0 ~ 5 part, puts in planetary ball mill, control stirring velocity at 150 ~ 300r/min, stirred at ambient temperature 10 ~ 30min, the mixture obtained is described thermo-stabilizer mixture.
Wherein, stearate soap is calcium stearate (CaSt
2) and Zinic stearas (ZnSt
2) the mixture of one or both.Auxiliary heat stabilizer is tetramethylolmethane (PER), diphenylpropane-1,3-dione(DPPO) (DBM), epoxy soybean oil (ESBO), any one or a few of triphenyl phosphite (TPPi).Internal lubricant is the mixture of any one or the two of stearic acid (HSt) and butyl stearate (BS).External lubricant is the mixture of the one or both of paraffin and polyethylene wax.
The embody rule method of above-mentioned heat stabilizer for PVC mixture is: add the thermo-stabilizer mixture of 2 ~ 5 mass parts and the o-phthalic acid dibutyl ester (DOP) of 10 ~ 50 mass parts in the PVC of every 100 mass parts, through mixing, mixingly makes PVC product.
Above-mentioned zinc-base thermo-stabilizer also can directly be applied, and adds the o-phthalic acid dibutyl ester (DOP) of 2 ~ 5 mass parts zinc-base thermo-stabilizers and 10 ~ 50 mass parts in the PVC of every 100 mass parts, through mixing, mixingly makes PVC product.
Polyvinyl chloride resin heat stability testing comprises following four aspects:
1) PVC sample preparation: by 100 mass parts polyvinyl chloride resins, after the composite thermal stabilizer of 10 ~ 50 mass parts DOP and 2 ~ 5 mass parts is placed in the artificial mixed grinding 5min of mortar, mixing 5min in the two rod mills throwing into 170 DEG C, obtains the antibacterial polyvinyl chloride resin sample that 0.5mm is thick.
2) static-aging test: the small pieces PVC sample obtained being cut into some 3cm × 3cm, puts into 180 DEG C of baking ovens, takes out small pieces every 10min, until from the complete blackening of small pieces of same PVC sample.This test the quality of initial stage form and aspect of qualitative evaluation polyvinyl chloride resin and zinc can burn the length of time.
3) de-HCl test: the particle PVC sample obtained being cut into 2mm × 2mm, accurately takes 0.5g and is placed in thermal destruction instrument and tests, temperature 180 DEG C, gas velocity 7Lh
-1, obtain the time dependent de-HCl graphic representation of specific conductivity, according to German standard DIN53381-1-1983, obtain induction time and the steady time of corresponding PVC sample.The length difference quantitative evaluation thermo-stabilizer initial stage thermostable effect of induction time and steady time and the quality of long-acting thermostable effect in this experiment.
4) anti-microbial property test: the small pieces PVC sample obtained being cut into some 3cm × 3cm, the antibacterial ability of prepared antibacterial PVC sample is evaluated according to the contact process in revised U.S. textile chemist AATCC100-1999 anti-microbial property testing standard, wherein, bacterium used be belong to Gram-negative bacteria intestinal bacteria (
escherichiaColi, CMCC44103) and belong to gram-positive streptococcus aureus (
staphylococcusAureus, ATCC6538).During test, by 50 μ L bacterial suspensions (containing the TX-100 of 2wt%, wherein e. coli concentration 7 × 10
4cFU, streptococcus aureus concentration 4 × 10
4cFU) above-mentioned die surfaces is placed in, then cover on it with same small pieces, to guarantee abundant contact, after the contact phase of 24h, whole sample is transferred in 5mL deionized water, and violent vortex 1min, ultrasonic 5min, make the bacteria distribution sticking to sample surfaces in solution, gained solution, after gradient dilution, gets the diluent of 100 μ L on agar plate, cultivate 24h under 37 ° of C after, bacterium colony is counted, if without bacterium colony, then can assert this duration sterilizing rate 100%, antibacterial effect is good, get the shortest antibacterial time, evaluating combined auxiliary agent germ resistance.
The present invention is by introducing polydentate ligand H
2l and Zinc diacetate dihydrate synthesize a kind of Schiff base zinc metal complexes Zn
3(HL)
2(CH
3cOO)
4, and prepare zinc-base composite thermal stabilizer with this, can at PVC hot-work stage and Zn
2+coordination, thus suppress ZnCl
2concentration.Synthesis of the present invention and complex process are simply, with low cost, safety and environmental protection.
Thermo-stabilizer mixture of the present invention, while taking into account certain initial stage form and aspect, be conducive to postponing zinc and burn phenomenon generation, improve the long-acting thermostability of polyvinyl chloride resin, and anti-microbial property is excellent, antimicrobial efficiency is high.
Test result shows: the polyvinyl chloride resin initial stage form and aspect containing thermo-stabilizer mixture of the present invention are white; It is 90min ~ 150min that zinc burns the time; Induction time is 0.82h ~ 1.21h, and steady time is 0.85h ~ 1.27h.Meanwhile, containing the polyvinyl chloride resin of thermo-stabilizer mixture of the present invention, after contacting with inoculated bacteria, in 24h, can 97% be reached to the sterilizing rate of intestinal bacteria and streptococcus aureus.
Accompanying drawing explanation
Fig. 1 is Zn in the present invention
3(HL)
2(CH
3cOO)
4synthetic route chart;
Fig. 2, Fig. 3 are H in the present invention
2l and Zn
3(HL)
2(CH
3cOO)
4proton nmr spectra;
Fig. 4 is H in the present invention
2l and Zn
3(HL)
2(CH
3cOO)
4infrared spectra comparison diagram; (a) H
2the infrared spectra of L; (b) Zn
3(HL)
2(CH
3cOO)
4infrared spectra.
Embodiment
Below in conjunction with Application Example, the present invention is further described.
Embodiment 1: by 100gPVC resin, 20gDOP and 5gZn
3(HL)
2(CH
3cOO)
4mixture according to above PVC sample preparation methods, preparation PVC sample, and according to the thermally-stabilised and anti-microbial property of above testing standard test.Concrete outcome is in table 1.
Embodiment 2: mixture recipes: 100gPVC resin, 20gDOP and 5g composite thermal stabilizer (i.e. thermo-stabilizer mixture).Preparation PVC sample, testing method and data list are with embodiment 1.Wherein, composite thermal stabilizer contains: 3.8gZn
3(HL)
2(CH
3cOO)
4and 1.2gPER.
Embodiment 3: mixture recipes: 100gPVC resin, 20gDOP and 5g composite thermal stabilizer.Preparation PVC sample, testing method and data list are with embodiment 1.Wherein, composite thermal stabilizer contains: 3.8gZn
3(HL)
2(CH
3cOO)
4, 0.8gPER and 0.4gDBM.
Embodiment 4: mixture recipes: 100gPVC resin, 20gDOP and 5g composite thermal stabilizer.Preparation PVC sample, testing method and data list are with embodiment 1.Wherein, composite thermal stabilizer contains: 2.0gZn
3(HL)
2(CH
3cOO)
4, 0.6gPER, 0.8gHSt, 0.6gBS, 0.4g paraffin and 0.6g polyethylene wax.
Embodiment 5: mixture recipes: 100gPVC resin, 20gDOP and 5g composite thermal stabilizer.Preparation PVC sample, testing method and data list are with embodiment 1.Wherein, composite thermal stabilizer contains: 1.0gZn
3(HL)
2(CH
3cOO)
4, 1.0gZnSt
2, 2.0gCaSt
2, 0.4gDBM and 0.6gESBO.
Embodiment 6: mixture recipes: 100gPVC resin, 20gDOP and 5g composite thermal stabilizer.Preparation PVC sample, testing method and data list are with embodiment 1.Wherein, composite thermal stabilizer contains: 1.4gZn
3(HL)
2(CH
3cOO)
4, 1.4gZnSt
2, 0.7gCaSt
2, 0.1gDBM, 0.1gESBO, 0.3gHST, 0.4gBS, 0.3g paraffin and 0.3g polyethylene wax.
Embodiment 7: mixture recipes: 100gPVC resin, 20gDOP and 5g composite thermal stabilizer.Preparation PVC sample, testing method and data list are with embodiment 1.Wherein, composite thermal stabilizer contains: 1.3gZn
3(HL)
2(CH
3cOO)
4, 0.7gZnSt
2, 1.3gCaSt
2, 0.6gTPPi, 0.6gHST and 0.5g paraffin.
Embodiment 8: mixture recipes: 100gPVC resin, 20gDOP and 5g composite thermal stabilizer.Preparation PVC sample, testing method and data list are with embodiment 1.Wherein, composite thermal stabilizer contains: 0.8gZn
3(HL)
2(CH
3cOO)
4, 1.5gZnSt
2, 0.8gCaSt
2, 1gBS, 0.6gHSt and 0.3g polyethylene wax.
Embodiment 9: mixture recipes: 100gPVC resin, 20gDOP and 5g composite thermal stabilizer.Preparation PVC sample, testing method and data list are with embodiment 1.Wherein, composite thermal stabilizer contains: 1.4gZn
3(HL)
2(CH
3cOO)
4, 1.4gZnSt
2, 0.8gCaSt
2, 0.5gHSt, 0.4gBS and 0.5g polyethylene wax.
Embodiment 10: mixture recipes: 100gPVC resin, 20gDOP and 5g composite thermal stabilizer.Preparation PVC sample, testing method and data list are with embodiment 1.Wherein, composite thermal stabilizer contains: 1.5gZn
3(HL)
2(CH
3cOO)
4, 1.5gZnSt
2, 0.4gPER, 0.4gHST, 0.4gBS, 0.4g paraffin and 0.4g polyethylene wax.
Embodiment 11: mixture recipes: 100gPVC resin, 20gDOP and 5g composite thermal stabilizer.Preparation PVC sample, testing method and data list are with embodiment 1.Wherein, composite thermal stabilizer contains: 1.5gZn
3(HL)
2(CH
3cOO)
4, 1.5gCaSt
2, 0.4gPER, 0.4gHST, 0.4gBS, 0.4g paraffin and 0.4g polyethylene wax.
Reference examples: mixture recipes: 100gPVC resin, 20gDOP and 5g composite thermal stabilizer.Preparation PVC sample, testing method and data list are with embodiment 1.The composite thermal stabilizer of reference examples contains: 1.5gZnSt
2, 1.5gCaSt
2, 0.4gPER, 0.4gHST, 0.4gBS, 0.4g paraffin and 0.4g polyethylene wax.
Table 1 tests for carrying out static-aging test, de-HCl test and anti-microbial property to PVC sample in embodiment 1 ~ 11 and reference examples the synthesis result obtained:
The thermally-stabilised test result of PVC sample in table 1 embodiment 1 ~ 11
Be not difficult to find out from above-mentioned test result, Zn
3(HL)
2(CH
3cOO)
4can with CaSt
2, ZnSt
2, PER, DBM, ESBO, and traditional heat stabilizer for PVC such as TPPi produces good synergy, also at HSt, BS, can play thermostable effect under the PVC inside and outside lubricant agent existent condition that paraffin and polyethylene wax etc. are traditional.Polyvinyl chloride resin initial stage form and aspect containing thermo-stabilizer mixture of the present invention are white, and it is 90min ~ 150min that zinc burns the time; Induction time is 0.82h ~ 1.21h, and steady time is 0.85h ~ 1.27h.
Meanwhile, anti-microbial property test result shows, adds Zn separately
3(HL)
2(CH
3cOO)
4and add Zn
3(HL)
2(CH
3cOO)
4with all samples of other auxiliary agent, when being when contacting 24h, all can killing the bacterium of more than 97%, and not add Zn
3(HL)
2(CH
3cOO)
4sample 24h after sterilizing rate less than 10%, can think there is no sterilizing ability, this means Zn
3(HL)
2(CH
3cOO)
4sterilization effect obvious.
To sum up analyze, this thermo-stabilizer mixture applied range that the present invention announces, while guarantee initial stage form and aspect, burn phenomenon in suppression zinc to occur, improving the long-acting thermostability of PVC sample and improve the aspects such as PVC sample anti-microbial property and have a clear superiority in, is a kind of novel composite stabilizer with anti-microbial property.
Claims (10)
1. there is a long-acting zinc-base thermo-stabilizer for anti-microbial property, it is characterized in that: this zinc-base thermo-stabilizer adopts the Schiff's base N shown in chemical formula-I
1, N
3(code name is H to-bis-(salicylic aldehyde) contracting diethylenetriamine
2l) one as part and Zinc diacetate dihydrate synthesis contains zinc product, and its chemical constitution is Zn
3(HL)
2(CH
3cOO)
4.
2. a synthetic method for long-acting zinc-base thermo-stabilizer described in claim 1, is characterized in that comprising:
Step 1: synthesis N
1, N
3(code name is H to-bis-(salicylic aldehyde) contracting diethylenetriamine
2l)
Get in the 25ml methylene dichloride that 2.06g diethylenetriamine is dissolved in constant pressure funnel, at room temperature by it with the dichloromethane solution of the speed of 50ml/h instillation 77.5g salicylic aldehyde, keep room temperature reaction 2-3h to obtain yellow solution afterwards; Suction filtration at 313K temperature, then cools product and obtains yellow solid H at 280K temperature
2l; Wherein, 4.88g salicylic aldehyde is dissolved in 50ml methylene dichloride and obtains by the dichloromethane solution of described salicylic aldehyde;
Step 2: synthesis zinc-base thermo-stabilizer Zn
3(HL)
2(CH
3cOO)
4
Get the H of 3.11g
2l is dissolved in 50ml ethyl acetate, adds the two acetate hydrate zinc of 2.19 ~ 3.29g, reacts under 318K temperature, agitation condition, and suction filtration is separated and obtains crude product; Then use 20ml ethyl acetate (or methylene dichloride), 20ml water, 20ml ethyl acetate (or methylene dichloride) to wash three times respectively, under 318K temperature condition, vacuum-drying obtains light-yellow precipitate thing, i.e. Zn
3(HL)
2(CH
3cOO)
4.
3. synthetic method according to claim 2, is characterized in that: in step 1, and described methylene dichloride ethyl acetate or ethanol substitute.
4.PVC thermo-stabilizer mixture, comprising: chemical constitution is Zn
3(HL)
2(CH
3cOO)
4zinc-base thermo-stabilizer 5 ~ 10 parts, stearate soap 0 ~ 15 part, auxiliary heat stabilizer 1 ~ 3 part, internal lubricant 5 ~ 7 parts, external lubricant 0 ~ 5 part.
5. thermo-stabilizer mixture according to claim 4, is characterized in that: described stearate soap is the mixture of the one or both of calcium stearate and Zinic stearas.
6. thermo-stabilizer mixture according to claim 4, is characterized in that: described auxiliary heat stabilizer is tetramethylolmethane, diphenylpropane-1,3-dione(DPPO), epoxy soybean oil, any one or a few of triphenyl phosphite.
7. thermo-stabilizer mixture according to claim 4, is characterized in that: described internal lubricant is the mixture of any one or the two of stearic acid and butyl stearate.
8. thermo-stabilizer mixture according to claim 4, is characterized in that: described external lubricant is the mixture of the one or both of paraffin and polyethylene wax.
The 9.PVC application of thermo-stabilizer mixture, adds the thermo-stabilizer mixture of 2 ~ 5 mass parts and the o-phthalic acid dibutyl ester of 10 ~ 50 mass parts in the PVC of every 100 mass parts, through mixing, mixingly make PVC product.
10. the application of zinc-base thermo-stabilizer according to claim 1, adds the o-phthalic acid dibutyl ester of 2 ~ 5 mass parts zinc-base thermo-stabilizers and 10 ~ 50 mass parts in the PVC of every 100 mass parts, through mixing, mixingly make PVC product.
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| CN105802074A (en) * | 2016-04-19 | 2016-07-27 | 赖树兴 | Heat-resistant PVC |
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| CN107337876A (en) * | 2017-07-31 | 2017-11-10 | 清华大学深圳研究生院 | A kind of zinc-base heat stabilizer, its preparation method and heat stabilizer compound |
| CN113502014A (en) * | 2021-09-13 | 2021-10-15 | 中国科学院宁波材料技术与工程研究所 | Antibacterial agent and preparation method and application thereof |
| CN114989544A (en) * | 2022-07-01 | 2022-09-02 | 广东金毅科技股份有限公司 | Odorless high-transparency low-migration PVC material, blood transfusion tube and preparation method thereof |
| WO2024045679A1 (en) * | 2022-08-29 | 2024-03-07 | 清华大学 | Zn-based organic coordination nanoparticles and preparation method therefor, photoresist composition, and use thereof |
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| CN105802074A (en) * | 2016-04-19 | 2016-07-27 | 赖树兴 | Heat-resistant PVC |
| CN105885087A (en) * | 2016-04-19 | 2016-08-24 | 赖树兴 | Novel PVC heat stabilizer and preparation method thereof |
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| CN105885087B (en) * | 2016-04-19 | 2018-04-13 | 东莞市宏福新材料有限公司 | Pvc heat stabilizer and preparation method thereof |
| CN107337876A (en) * | 2017-07-31 | 2017-11-10 | 清华大学深圳研究生院 | A kind of zinc-base heat stabilizer, its preparation method and heat stabilizer compound |
| CN107337876B (en) * | 2017-07-31 | 2019-05-24 | 清华大学深圳研究生院 | A kind of zinc-base heat stabilizer, preparation method and heat stabilizer compound |
| CN113502014A (en) * | 2021-09-13 | 2021-10-15 | 中国科学院宁波材料技术与工程研究所 | Antibacterial agent and preparation method and application thereof |
| CN113502014B (en) * | 2021-09-13 | 2021-11-23 | 中国科学院宁波材料技术与工程研究所 | Antibacterial agent and preparation method and application thereof |
| CN114989544A (en) * | 2022-07-01 | 2022-09-02 | 广东金毅科技股份有限公司 | Odorless high-transparency low-migration PVC material, blood transfusion tube and preparation method thereof |
| CN114989544B (en) * | 2022-07-01 | 2024-04-02 | 广东金毅科技股份有限公司 | Odorless high-transparency low-migration PVC material, blood transfusion tube and preparation method thereof |
| WO2024045679A1 (en) * | 2022-08-29 | 2024-03-07 | 清华大学 | Zn-based organic coordination nanoparticles and preparation method therefor, photoresist composition, and use thereof |
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