CN107501535A - Zn complex catalyst of PLA and preparation method thereof is prepared for ring-opening polymerisation - Google Patents
Zn complex catalyst of PLA and preparation method thereof is prepared for ring-opening polymerisation Download PDFInfo
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- CN107501535A CN107501535A CN201710690953.9A CN201710690953A CN107501535A CN 107501535 A CN107501535 A CN 107501535A CN 201710690953 A CN201710690953 A CN 201710690953A CN 107501535 A CN107501535 A CN 107501535A
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- Prior art keywords
- complex
- lactide
- pla
- opening polymerization
- ring
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- 238000007151 ring opening polymerisation reaction Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 title abstract description 7
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 title description 2
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 7
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- FEQLQOCMMPKONI-UHFFFAOYSA-N toluene 1H-1,2,4-triazole Chemical group CC1=CC=CC=C1.N1N=CN=C1 FEQLQOCMMPKONI-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- -1 hydrogen Potassium oxide Chemical class 0.000 claims description 2
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical class C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910001950 potassium oxide Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 3
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 22
- 238000010586 diagram Methods 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000005564 crystal structure determination Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GTTYPHLDORACJW-UHFFFAOYSA-N nitric acid;sodium Chemical compound [Na].O[N+]([O-])=O GTTYPHLDORACJW-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011155 quantitative monitoring Methods 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- JGPSMWXKRPZZRG-UHFFFAOYSA-N zinc;dinitrate;hexahydrate Chemical class O.O.O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JGPSMWXKRPZZRG-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses Zn complex catalyst that PLA is prepared for ring-opening polymerisation and preparation method thereof, it is related to PLA catalyst field.Its chemical formula is [Zn5(btb)2(1,4‑NDC)4(μ 3‑OH)2], btb is two (methyl of 1,2,4 triazole 1) benzene parts in formula, and Isosorbide-5-Nitrae NDC is Isosorbide-5-Nitrae naphthalenedicarboxylic acid root anion,μ 3OH is hydroxyl bridging.The synthetic method yield that the present invention shows is high, favorable reproducibility；The crystal purity of gained is high, and the heat endurance having had.The catalytic activity that a kind of Zn complex has had to catalyzing ring-opening polymerization of lactide, the PLA weight average molecular weight of preparation can be applied in medical macromolecular materials field more than 30,000.
Description
Technical field
The present invention relates to PLA catalyst field, and in particular to a kind of Zn complex and preparation method thereof and catalysis third are handed over
The application of ester body ring-opening polymerisation.
Background technology
PLA (PLA, also known as polylactide), be it is a kind of be in light yellow or transparence aliphatic polyester family macromolecule
Material, density are about 1.25g/cm3, it is nonirritant, it is to be synthesized into by the lactic acid of biofermentation production through artificial chemistry.PLA
, can the most final decline in the presence of microorganism or enzyme in natural environment with good biocompatibility and biodegradability
Solve as carbon dioxide and water, realize the circulation in nature, be preferable Green Polymer Material.Prepared by PLA various
Film, sheet material and fiber product be widely used in clothes, weaving, packaging, agricultural, forestry, civil construction, medical and hygiene article and
The fields such as daily living article.
Lactic acid direct polycondensation is a kind of relatively simple method for preparing PLA, but typically can only obtain PLA's by this method
Oligomer (number-average molecular weight is less than 5000) molecular weight, molecular weight distribution is wider, and if polymerization temperature is higher than 180 DEG C, also
Coloured product can be caused to deepen, so as to limit its further application.Up to the present, the PLA of HMW mainly passes through
Lactide under initiator existence condition ring-opening polymerisation be made (Thomas C.M.Chem.Soc.Rev.2010,39,165-
173).Tin compound, such as stannous chloride, butter of tin and stannous octoate, it is considered to be trigger lactide body ring-opening polymerisation
Prepare that PLA is most widely used and the higher catalyst of efficiency, monomer conversion is high in course of reaction, product for racemization, but it
There is certain cytotoxicity, hinder applications of the PLA in medical polymer Material Field.Transition metal such as zinc, titanium and zirconium
Deng having relatively low toxicity, wherein zinc also has strong Lewis acid, in recent years, third is studied based on Zn complex catalyst
The ring-opening polymerisation of lactide attracts attention (Chen H.-Y., Huang B.-H., Lin C.-C.Macromolecules
2005,38,5400–5405；Fliedel C.,Vila-Vicosa D.,Calhorda M.J.,Dagorne S.,Aviles
T.ChemCatChem 2014,6,1357–1367).But it is difficult to find suitable an organic ligand and zinc ion coordination at present
The ring-opening polymerisation of obtained complex energy efficient catalytic lactide, while the characteristics of take into account molecular weight high and narrowly distributing.Meanwhile zinc
The stability of complex is also to restrict its big difficult point applied in lactide system is catalyzed.Therefore, for synthesizing and exploring
Thermostabilization, the research of high catalytic activity Zn complex have wide space, are also aliphatic polyester series high polymer material future
Powerful vitality is injected in large-scale production.
The content of the invention
The invention aims to further expand less toxic zinc class complex applied to catalysis lactide body open loop to gather
Close and prepare PLA, disclose a kind of Zn complex and preparation method thereof and catalyzing ring-opening polymerization of lactide prepares PLA application.The zinc
Complex has preferable heat endurance, and its synthetic method is easy to operate, and yield is high, favorable reproducibility, to lactide body open loop
It polymerize the catalytic activity having had, the PLA weight average molecular weight of preparation has potential more than 30,000 in medical macromolecular materials field
Application.
A kind of Zn complex applied to catalyzing ring-opening polymerization of lactide of the invention, its chemical formula is [Zn5(btb)2(1,4-
NDC)4(μ3-OH)2], btb is two (1,2,4- triazole -1- methyl) benzene parts in formula, and Isosorbide-5-Nitrae-NDC is Isosorbide-5-Nitrae-naphthalenedicarboxylic acid root
Anion, μ3- OH is hydroxyl bridging.
A kind of Zn complex applied to catalyzing ring-opening polymerization of lactide of the invention, it is characterised in that its secondary building unit
For：Crystal belongs to monoclinic system, space group P21/ c, molecular formula C72H54N12O20Zn5, molecular weight 1734.12；Structure cell is joined
Number is：α=90 °, β=117.229 °, γ=90 ° are brilliant
Cell space accumulatesBasic structure is a three-dimensional net structure.
The preparation method of described Zn complex, it is characterised in that carry out as steps described below：By zinc nitrate hexahydrate, two
(1,2,4- triazole -1- methyl) benzene, Isosorbide-5-Nitrae-naphthalenedicarboxylic acid, potassium hydroxide and water is put into reactor, after closing, in 180 DEG C
Reaction 72 hours；Reaction cools to room temperature after terminating, and obtains a kind of crystal of Zn complex, then use acetone and methanol successively
Washing, dry and be made.
In above-mentioned technical proposal, in molar ratio, zinc nitrate hexahydrate:Two (1,2,4- triazole -1- methyl) benzene:1,4- naphthalenes
Dioctyl phthalate:Potassium hydroxide=2:1:2:4.
In above-mentioned technical proposal, every 0.1 mM two (1,2,4- triazole -1- methyl) benzene correspond to 7 milliliters of water.
The method that described Zn complex catalyzing ring-opening polymerization of lactide prepares PLA, is carried out as steps described below：By described in
Zn complex and lactide are added in Schlenk pipes, are warming up to 180 DEG C, body ring-opening polymerization 60 hours, poly- breast are made
Acid, pass through simultaneously1H NMR quantitative analyses obtain lactide conversions up to 99%.
Wherein Zn complex and lactide mol ratio are 1:4000；Gained PLA weight average molecular weight is 33096, Ke Yiying
Used in medical macromolecular materials field.
Advantages of the present invention：The synthetic method of the present invention is easy to operate, and yield is high, favorable reproducibility.Zn complex heat is steady
Qualitative good, the catalytic activity having had to lactide open loop, the PLA weight average molecular weight of preparation can be applied medical more than 30,000
Polymeric material field.
Brief description of the drawings
Wherein Fig. 1 is the coordination context diagram of zinc ion in Zn complex；
Wherein Fig. 2 is the 3-D solid structure schematic diagram of Zn complex；
Wherein Fig. 3 is the three-dimensional topology network diagram of Zn complex；
Wherein Fig. 4 is the powder diffraction schematic diagram of Zn complex；
Wherein Fig. 5 is the thermogravimetric schematic diagram of Zn complex；
Wherein Fig. 6 is Zn complex catalyzing ring-opening polymerization of lactide conversion ratio and reaction time schematic diagram.
Embodiment
The preparation of the Zn complex of experimental example 1：
By 59.4 milligrams of (0.2 mM) zinc nitrate hexahydrates, 24.0 milligrams (0.1 mM) two (1,2,4- triazoles-
1- methyl) benzene and 43.2 milligrams of (0.20 mM) 1,4- naphthalenedicarboxylic acids, 22.4 milligrams of (0.4 mM) potassium hydroxide and 7 millis
Rise deionized water to be added sequentially to seal in the stainless steel autoclave of 15 milliliters of polytetrafluoroethyllining linings, be warming up to 180 DEG C,
Constant temperature 72 hours, after being then cooled to room temperature with 5 DEG C per hour of speed, obtain the yellowish color lump for being adapted to X-ray single crystal diffraction
Shape crystal, then washed successively with acetone and methanol, dry and a kind of Zn complex is made, and yield 73% (63.3 milligrams, based on two
(1,2,4- triazole -1- methyl) benzene).
Main infrared absorption peak is (KBr/cm–1)：3644w,3571w,3447w,3137w,3123w,3102w,
1618s,1590m,1570m,1531m,1510m,1454m,1361s,1281m,1259m,1209w,1160w,1131m,933w,
825m,793m,691w,506w。
Test the sign of a Zn complex
(1) crystal structure determination of Zn complex
Crystal structure determination uses Bruker Apex II CCD diffractometers, under 293 (2) K, with through graphite monochromatised
Mo K alpha raysPoint diffraction is collected with ω scan modes, the data of collection are used in combination by SAINT programe reductions
SADABS methods carry out semiempirical absorption correction.Structure elucidation and refine be respectively adopted SHELXTL programs SHELXS and
SHELXL is completed, by complete matrix least square method to F2It is modified to obtain the coordinate and anisotropy of whole non-hydrogen atoms
Parameter.All hydrogen atoms are fixed on parent during structure refinement by theory, are assigned more slightly larger than parent displacement parameter
The isotropism displacement parameter of (C-H, 1.2 or O-H, 1.5 times).Detailed axonometry data are shown in Table 1.Structure is shown in Fig. 1-3.Figure
1：The coordination context diagram of zinc ion in Zn complex；Fig. 2：The 3-D solid structure schematic diagram of Zn complex；Fig. 3：Zn complex
Three-dimensional topology network diagram.
(2) the phase purity of Zn complex characterizes
The powder diffraction of Zn complex, which characterizes, shows that it has reliable phase purity, gathers for it as catalysis lactide open loop
The application of conjunction provides guarantee.See Fig. 4.(INSTRUMENT MODEL：Rigaku D/Max-2500)
(3) heat endurance of Zn complex characterizes
The heat endurance of Zn complex can be characterized by thermogravimetric analyzer, the results showed that, the Zn complex skeleton has
High heat endurance, 310 DEG C can be stabilized to.See Fig. 5：The thermogravimetric schematic diagram of Zn complex.(INSTRUMENT MODEL：NETZSCH/TG
209F3)
Test two Zn complex catalyzing ring-opening polymerization of lactide performance studies
1000 milligrams of lactides (6.9 mMs) and 3.0 milligrams of Zn complexes (0.0017 mM) are added to
In Schlenk pipes, 180 DEG C of reactions are warming up to, PLA, warp are made after 60 hours1H NMR quantitative analyses obtain lactide conversions
Up to 99%.Meanwhile by taking 30.0 milligrams of sample every time, and be dissolved in 0.5 milliliter of deuterochloroform, pass through1H NMR Quantitative Monitorings
The conversion ratio of lactide and the relation in reaction time, are shown in Fig. 6：Zn complex catalyzing ring-opening polymerization of lactide reaction conversion ratio with it is anti-
Answer time diagram.(INSTRUMENT MODEL：Bruker Avance 400MHz)
Test three Zn complexes catalysis lactide and prepare PLA
1000 milligrams of lactides (6.9 mMs) and 3.0 milligrams of Zn complexes (0.0017 mM) are added to
In Schlenk pipes, at 180 DEG C, insulation reaction 60 hours, it is subsequently cooled to room temperature and obtains white products PLA.
Test the measure of four PLA molecular weight
5.0 milligrams of PLA are taken, are dissolved in the DMF solution that 5 milliliters of nitric acid sodium contents are 0.07 mol/L,
Teflon membrane filter filtering by 0.4 micron pore size, taking 20 microlitres to be added to Shimadzu (Japan) system, " LC-20AD GPC " enter
In sample device, by the way that weight average molecular weight is calculated as 33096.
Test condition：40 DEG C of column temperature；Eluent：N,N-dimethylformamide dissolved with 5 mM/ls of sodium nitrate；Stream
Fast 0.8 ml/min；Detector：RI detectors；Correction：The use of weight average molecular weight is respectively 2.2,7.9,23.0,49.4 and
Poly- (methyl methacrylate) of 99.4kDa five kinds of various criterions carries out molecular weight calibration.
The predominant crystal data of the Zn complex of table 1
Claims (7)
1. a kind of Zn complex applied to catalyzing ring-opening polymerization of lactide, it is characterised in that its chemical formula is [Zn5(btb)2(1,
4-NDC)4(μ 3-OH)2], btb is two (1,2,4- triazole -1- methyl) benzene parts in formula, and Isosorbide-5-Nitrae-NDC is Isosorbide-5-Nitrae-naphthalenedicarboxylic acid
Root anion,μ 3- OH is hydroxyl bridging.
A kind of 2. Zn complex applied to catalyzing ring-opening polymerization of lactide according to claim 1, it is characterised in that its
Secondary building unit is：Crystal belongs to monoclinic system, and space group isP21/c, molecular formula C72H54N12O20Zn5, molecular weight is
1734.12；Cell parameter is：A=15.335 (1), b=15.646 (1), c=16.419 (1), α=90 °, β
=117.229 °, γ=90 °, unit cell volume is 3502.9 (5)3；Basic structure is a three-dimensional net structure.
3. a kind of preparation method of Zn complex applied to catalyzing ring-opening polymerization of lactide described in claim 1, its feature
It is to carry out as steps described below：By zinc nitrate hexahydrate, two (1,2,4- triazole -1- methyl) benzene, 1,4- naphthalenedicarboxylic acids, hydrogen
Potassium oxide and water are put into reactor, after closing, are reacted 72 hours in 180 DEG C；Reaction cools to room temperature after terminating, and obtains described
A kind of crystal of Zn complex, then washed successively with acetone and methanol, dry and be made.
4. a kind of preparation method of Zn complex applied to catalyzing ring-opening polymerization of lactide according to claim 3, its
It is characterised by molar ratio, zinc nitrate hexahydrate:Two (1,2,4- triazole -1- methyl) benzene:1,4- naphthalenedicarboxylic acids:Hydrogen-oxygen
Change potassium=2: 1 : 2 : 4.
5. a kind of preparation method of Zn complex applied to catalyzing ring-opening polymerization of lactide according to claim 3, its
It is characterised by：The corresponding 7 milliliters water of every 0.1 mM two (1,2,4- triazole -1- methyl) benzene.
6. the method that the Zn complex catalyzing ring-opening polymerization of lactide described in claim 1 prepares PLA, it is characterised in that press
Carried out according to following step：The Zn complex and lactide are added in Schlenk pipes, are warming up to 180 DEG C, body open loop gathers
Reaction 60 hours is closed, PLA is made, passes through simultaneously1H NMR quantitative analyses obtain lactide conversions up to 99%.
7. the method that Zn complex catalyzing ring-opening polymerization of lactide according to claim 6 prepares PLA, its feature exist
In：Zn complex and lactide mol ratio are 1: 4000；Gained PLA weight average molecular weight is 33096, can apply and cure
Use polymeric material field.
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