CN108676021B - A kind of zinc catalyst and preparation method thereof and the application in lactone ring opening polymerization - Google Patents

A kind of zinc catalyst and preparation method thereof and the application in lactone ring opening polymerization Download PDF

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CN108676021B
CN108676021B CN201810343876.4A CN201810343876A CN108676021B CN 108676021 B CN108676021 B CN 108676021B CN 201810343876 A CN201810343876 A CN 201810343876A CN 108676021 B CN108676021 B CN 108676021B
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polymerization
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CN108676021A (en
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介素云
胡倩
李伯耿
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Zhejiang University ZJU
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    • 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
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
    • 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
    • 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
    • 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
    • C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86

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  • 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

Application the invention discloses a kind of preparation method of Zn complex and its as catalyst in the ring-opening polymerization of internal ester monomer, the catalyst system use metallic zinc for the center of complex catalyst, and ligand is the tridentate ligand of NNO composition；The zinc catalyst is first mixed with a certain amount of lithium alkylide in a solvent, reacts in-situ preparation alkyl Zn complex, internal ester monomer is added and carries out polymerization reaction；Zn complex of the invention goes out to show excellent catalytic activity in the ring-opening polymerization of 6-caprolactone, and since metallic zinc is as microelement possessed by human body itself, it is non-toxic to humans, therefore be with a wide range of applications for polyester material prepared by catalyst in medical field using the system.

Description

A kind of zinc catalyst and preparation method thereof and the application in lactone ring opening polymerization
Technical field
The invention belongs to chemical technology fields, are related to a kind of Zn complex catalyst and the catalyst in lactone open loop Application in polymerization reaction.
Background technique
In recent years, ever-increasing white pollution has become a serious environmental problem.The twentieth century forties with Come, the high molecular material based on petrochemical industry is greatly paid close attention to.Although these materials have plurality of advantages, have Two big disadvantages have to be solved.First is that the various plastic products made of polyolefin macromolecular compound are in the natural environment very Stablize, they are difficult to degrade in nature, lead to huge environmental pressure；In addition limited petroleum resources are largely consumed, will It will lead to the quick exhaustion of resource.Therefore, seek that resource is reproducible, environmental-friendly and biodegradable polymer mesh Before have become the hot spot of chemical field research.
There is good mechanical performance, water-disintegrable and life by the aliphatic polyester series material that lactone ring opening polymerization is prepared Object compatibility is a kind of promising petrochemical-based plastics substitute, is achieved in recent years in synthesis, manufacture and manufacture field very big Progress, and the application of these materials is more extensive, and practical application is from packaging field to more complicated biomedical apparatus.
The preparation method of aliphatic polyester mainly has condensation polymerization method and ring-opening polymerisation method etc..The raw material of condensation polymerization method at This is lower, and polymerizate is pure, does not need medium separation, but molecular weight of product is low, molecular weight distribution is wider, is unfavorable for material Stablize.And a kind of effective way of the ring-opening polymerisation method as synthesis polyester, the feature of active polymerization can make polymerization reaction And there is product controllability to have widened the application field of aliphatic polyester to improve the stability of material property.
According to the difference of catalyst, ring-opening polymerisation is divided into substantially: cationic polymerization, anionic polymerisation and " coordination-insert Enter " polymerization.The last century 80's, auspicious gentle phase field is tall and erect on the well of Tokyo Univ Japan third develops metal-porphyrin complexing System catalytic activity ring-opening polymerisation, the molecular number for generating polymer are consistent with the molecular number of complex compound, change monomer and complex compound Amount ratio can fully control the degree of polymerization of polymer, and molecular weight of product narrow distribution (Macromolecules, 1984,17(11):2217-2222.).Coordination ring-opening polymerisation as a result, gradually grows up, especially low toxicity, efficient, high selection Property catalyst system become academia research hot spot.Compared to the polymerization reaction of first two type, coordination polymerization has efficient, secondary The advantages that reaction is few and controllability is good.It is corresponding since different metal has different oxidationreduction abilities in complex Complex different catalytic activity is also shown in the ring-opening polymerisation of lactone.
Research and the catalytic activity of Different Complex are studies have shown that more inquire into the coordination of different coordination modes and metal Object, the active higher, efficiency of meeting and the better catalyst of selectivity, less toxic catalyst guarantee the good environment phase of gained resin Capacitive and potential medical value.The metal that can be used for internal ester monomer ring-opening polymerisation mainly has alkali metal (lithium, sodium, potassium), alkaline earth gold Category (magnesium, calcium etc.), group ivb metal (titanium, zirconium etc.), rare earth metal (yttrium, lanthanum etc.) and aluminium etc..
Metal complex catalyzed system has a few metals salt and remains on aliphatic polyester after ring-opening polymerization In product, it is difficult to dispel in the purifying of polymer completely, it is potential dangerous that this will be such that degradable high polymer material product exists Property, it is limited in the application of biomedicine field.In view of the deficiencies in the prior art, prepared using biological absorbable metal ion Catalyst system can solve this problem.Kricheldorf etc. has studied a large amount of metal salt catalysts with bioresorbable Agent, the wherein active highest of zinc lactate catalyzing ring-opening polymerization of lactide, obtained molecular weight of product narrow distribution.Zinc chloride can be with Be catalyzed caprolactone ring-opening polymerization, reaction mechanism meet coordination-insertion mechanism (J.Polym.Sci., Part A: Polym.Chem.,2000,159(1):247-258).Alkoxy iron can trigger the ring-opening polymerisation of lactide and caprolactone, this Reaction has good controllability, and the degree of polymerization of product is consistent with the molar ratio of monomer, initiator (J.Am.Chem.Soc.2002,124(16):4384-4393.).Alkoxy calcium can be catalyzed cyclic ester at room temperature Ring-opening polymerization, reaction rate are higher than aluminum alkoxide and alkoxy tin, and the molecular weight of polymerizate is consistent with theoretical value, molecule Amount distribution is less than 1.3 (Macromolecules, 2001,34 (12): 3863-3868).In view of cost and environment influence etc. because Element, a kind of catalyst system of the metal Zn complex as green can be used as catalyzing lactone monomer ring-opening polymerisation and preferably select.
The present invention has synthesized a series of Zn complex catalyst of ligand structures containing NNO, and is applied to catalyzing lactone open loop In polymerization, excellent catalytic activity is shown, prepared aliphatic poly ester material has structure-controllable, nontoxic, bio-compatible Property it is good the features such as, have extensive prospects for commercial application.
Summary of the invention
The object of the present invention is to provide a kind of zinc catalysts and preparation method thereof.
Further, the complex of the present invention containing metallic zinc has the following structure structure shown in formula:
Wherein, R1, R2, R3 are each independently selected from the alkyl or aryl of C1~C10 straight chain, branched structure, hydrogen in structure Atom or halogen atom.
Further, the R1 in structure preferably is selected from hydrogen atom, methyl, tert-butyl, chlorine atom, bromine atom or iodine atom.
R2 and R3 in structure preferably are selected from alkyl, phenyl or alkyl-substituted phenyl.
X in structure is preferable over the halogen atoms such as Br, Cl or acetate ion.
The present invention provides the preparation methods of the Zn complex of one of bis- (amino) phenoxy ligands Han 2,6-, including Following steps:
(preferably 1:2) is in trifluoro after hexamethylenetetramine is mixed with phenol or fortified phenol by the molar ratio of 1:2~2.5 It flows back in acetic acid solvent 12~28 hours (preferably 24 hours), after the HCl processing of 4M is added, organic extractant phase is added, washing, does It is dry, it removes solvent and obtains chemical compounds I after purification.Gained chemical compounds I is dissolved with dehydrated alcohol, 2~3 equivalents are added contains 2, The aniline (preferably 2.2 equivalents) and a few drop glacial acetic acid of 6- substituent group as catalyst, (preferably 50 DEG C) reaction 3 at 20~60 DEG C~ 9 hours (preferably 8 hours), certain solvent is removed under reduced pressure, with ice ethanol washing, drying, obtains bis- (imino group) benzene oxygen containing 2,6- Ligand, that is, compound ii of base.Compound ii is dissolved in methanol solvate, and the sodium borohydride (preferably 4 equivalents) that 2~4 equivalents are added is made For reducing agent, 6~18 hours (preferably 12 hours) are reacted at room temperature, are added water quenching to go out excess sodium borohydrate, are removed under reduced pressure certain molten Agent, liquid separation, organic phase dry, filter, and remove solvent and obtain the compound III of bis- (amino) phenoxy groups Han 2,6-.Compound III exists Ethyl alcohol is to react 2~12 hours (preferably 3 under 20~50 DEG C (preferably 25 DEG C) with zinc chloride by the molar ratio of 1:1 under solvent Hour), solvent is removed under reduced pressure and wash 3 times with poor solvent, obtains containing bis- (amino) phenoxy groups of 2,6- accordingly after drying and match The Zn complex of body.
A further object of the present invention is to provide application of the above-mentioned Zn complex in catalyzing lactone monomer ring-opening polymerisation.It will The Zn complex is first mixed with the lithium methide of 4 equivalents in a solvent, and reacting makes the Zn complex of in-situ preparation lithium alkylide, then plus Enter internal ester monomer and carries out polymerization reaction.The solvent by the organic solvents such as benzene, toluene, tetrahydrofuran, methylene chloride one kind or A variety of compositions.
The solvent is preferably toluene；The temperature of the polymerization reaction is preferably 30 DEG C.
Using Zn complex of the present invention as catalyst, after the lithium methide hybrid reaction of 4 equivalents is added, make 6-caprolactone 0 It polymerize under the conditions of~120 DEG C, the molar ratio of catalyst and caprolactone is 1:50~5000 (preferably 1:50~1000) when polymerization.
Using Zn complex of the present invention as catalyst, after the lithium methide hybrid reaction of 4 equivalents is added, the condition existing for alcohol Under polymerize 6-caprolactone under the conditions of 0~120 DEG C, when polymerization catalyst and alcohol and monomer mole ratio be 1:1~10:50~ 5000；The alcohol is C1~C10 straight chain, the alkylol of branch or cyclic structure or benzylalcohol (preferably benzylalcohol).
Catalyst preparation provided by the invention is convenient, property is stablized, while catalytic activity with higher, easily acquisition high score The aliphatic polyester of son amount and narrow ditribution is particularly suitable for catalysis caprolactone ring-opening polymerisation.By the control to polymeric reaction condition, The molecular size range that polymer can be regulated and controled, from thousands of tens of thousands of to ten.
Specific implementation method
Embodiment 1
The synthesis of ligand L 1 and zinc catalyst Zn1:
Reference literature (Synthesis, 1998,1998 (07): 1029-1032.), by p-methyl phenol (4.040g, It 37.3mmo1) is dissolved in 40ml trifluoroacetic acid, hexamethylenetetramine (10.600g, 75.6mmo1) is added portionwise, is stirred at 90 DEG C It mixes for 24 hours, solution becomes rufous from yellow.Reaction solution is poured into while hot in the HCl solution of 60ml 4M, 2h is stirred at room temperature, Drag has orange red grease to be precipitated.Continue the 4M HCl solution for adding 100ml, have white opacity generation in adition process, Stirring becomes clear state again.Acquired solution is poured into the separatory funnel of 500ml, is extracted with CH2Cl2 (100ml × 3), is closed And organic phase.It is washed respectively with 4M HCl solution, H2O, NaCl saturated solution (100ml × 3) later.The yellow liquid that will be obtained Dry with anhydrous Na 2SO4, being concentrated to get crude product is yellow oil.Silicagel column is crossed to purify to obtain the target for yellow powder Product 2- hydroxy-5-methyl base-isophthalic aldehyde.
Sequentially added in 100ml single necked round bottom flask 2- hydroxy-5-methyl base-isophthalic aldehyde (0.990g, 6.0mmol) and 40ml dehydrated alcohol and 2, in 6- dimethylaniline (99%, 1.769g, 14.5mmol), reaction is carried out by the 1:2 of raw material, wherein 2,6- dimethylaniline is slightly excessive.8h is reacted at 50 DEG C.A few drop glacial acetic acid are added dropwise as catalyst.Reaction solution is orange, reaction A large amount of orange powders are precipitated in the process.Orange powder is filtered, is washed 3 times with the dehydrated alcohol of ice.It is put into after filtrate concentrated by rotary evaporation Refrigerator overnight is precipitated yellow crystals and uses ice ethanol washing again again.Product 1.6789g, yield 75.3% is obtained.
By obtained 2,6- diformyl -4- methyl-phenoxv-(2,6- dimethylaniline) (1.52g, 4.10mmol) Crocus powder is added in 25ml anhydrous methanol, and the sodium borohydride (1.24g, 32.8mmol) of 4 equivalents is added under ice-water bath.It is molten Liquid becomes faint yellow from orange.Reaction 12h has pale yellow powder precipitation at room temperature.After reaction, water is added to remove extra boron Methanol is removed under reduced pressure in sodium hydride, is extracted with dichloromethane (30ml × 4), and saturated common salt water washing (100ml × 2) is added later The appropriate dry 6h of anhydrous sodium sulfate.It is spin-dried for solution and obtains yellow oil, obtain 1.623g canescence sample after the crystallization that adds diethyl ether. Vacuum drying, final product 1.446g, yield 94.7%.
The ligand L 1 (0.638g, 4.7mmol) of synthesis will be added in 50ml round-bottomed flask, is dissolved in 30ml dehydrated alcohol, adds Enter zinc chloride (1.744g, 4.7mmol) and stir 6hr at 50 DEG C, is evaporated filtrate, is washed with n-hexane and obtain three times faint yellow Solid Zn1 (1.081g, 45.4%), structural formula are as follows:
Embodiment 2
The synthesis of ligand L 2 and zinc catalyst Zn2:
In addition to raw material is using p-tert-butylphenol and hexamethylenetetramine, other operating procedures are the same as embodiment 1.It obtains Zn2 structural formula are as follows:
Embodiment 3
The synthesis of ligand L 3 and zinc catalyst Zn3:
In addition to raw material is using parachlorophenol and hexamethylenetetramine, other operating procedures are the same as embodiment 1.Obtained Zn3 knot Structure formula are as follows:
The Zn complex of the compounds of above-mentioned all preparations and the ligand containing NNO by NMR spectrum, infrared spectroscopy and The methods of elemental analysis is confirmed.
Embodiment 4
Zinc catalyst Zn1 (10.2mg, 0.02mmol) is added first in Schlenk bottles, three times with high pure nitrogen ventilation The solvent toluene that 2.5ml was purified is added afterwards, 1ml lithium methide (toluene solution of MeLi, 0.04mol/L) is added at 0 DEG C, makes [Zn1] 0/ [MeLi] 0=1/4 is slowly increased to room temperature reaction 2h, and the 6-caprolactone of 0.44ml, control reaction are added with syringe Temperature reacts 3min at 60 DEG C, and 0.5ml distilled water is added and terminates reaction, reaction solution is poured into n-hexane, adds appropriate N-hexane has polycaprolactone to be precipitated out, goes filtrate after standing 10min, adds a small amount of CH2CI2 dissolution polymer, adds Enter appropriate n-hexane and white solid be precipitated, repeatedly three times after, filtering is drained, and vacuum drying obtains polycaprolactone.Conversion ratio: 99%, number-average molecular weight Mn=20.9 × 103g/mol, molecular weight distribution D=1.57.
Embodiment 5
Zinc catalyst Zn1 (10.2mg, 0.02mmol) is added in Schlenk bottles under nitrogen protection, 1.78ml was purified Solvent toluene, 1ml lithium methide (toluene solution of MeLi, 0.08mol/L), make [Zn1] 0/ [MeLi] 0=1/4 (molar ratio, Similarly hereinafter), after reacting 2h at room temperature, the ε-CL of 0.66ml is added with syringe, makes [Zn1] 0=0.0058M, [Zn1] 0:[BnOH] 0:[ε-CL] 0=1:0:300.Polymerization reaction starts to carry out.In addition to additional description, it is molten that the total volume of polymerization reaction passes through adjusting The amount of agent toluene is controlled in 3.44ml.3min is reacted in 90 DEG C of reaction temperature of control, and distilled water is added and terminates reaction, reaction solution falls Enter in n-hexane and staticly settle, filter, filtrate is dissolved with methylene chloride, appropriate n-hexane is added, solid is precipitated, repeatedly After three times, filtering is drained, and vacuum drying obtains polycaprolactone.Conversion ratio: 100%, number-average molecular weight Mn=22.0 × 103g/ Mol, molecular weight distribution D=1.58.
Embodiment 6
Zinc catalyst Zn1 (10.2mg, 0.02mmol) is added in Schlenk bottles under nitrogen protection, 0.78ml was purified Solvent toluene, 1ml lithium methide (toluene solution of MeLi, 0.08mol/L), make [Zn5] 0/ [MeLi] 0=1/4 (molar ratio, Similarly hereinafter), after reacting 2h at room temperature, the Bian alcohol (toluene solution of BnOH, 0.1mol/L) and 0.66ml of 1ml are added with syringe ε-CL makes [Zn5] 0=0.0058M, [Zn1] 0:[BnOH] 0:[ε-CL] 0=1:5:300.Polymerization reaction starts to carry out.Except volume Outside external declaration, the total volume of polymerization reaction passes through the amount control for adjusting solvent toluene in 3.44ml.30 DEG C of reaction temperature of control, 30min is reacted, distilled water is added and terminates reaction, reaction solution is poured into n-hexane and staticly settled, and is filtered, by filtrate methylene chloride Dissolution is added appropriate n-hexane and solid is precipitated, repeatedly three times after, filtering is drained, and vacuum drying obtains polycaprolactone.Conversion Rate: 65.7%, number-average molecular weight Mn=3.17 × 103g/mol, molecular weight distribution D=1.07.
Embodiment 7
Zinc catalyst Zn1 (10.2mg, 0.02mmol) is added in Schlenk bottles under nitrogen protection, 2.13ml was purified Solvent toluene, 1ml lithium methide (toluene solution of MeLi, 0.08mol/L), make [Zn1] 0/ [MeLi] 0=1/4 (molar ratio, Similarly hereinafter), after reacting 2h at room temperature, the Bian alcohol (toluene solution of BnOH, 0.1mol/L) and 0.11ml of 1ml are added with syringe ε-CL makes [Zn1] 0=0.0058M, [Zn1] 0:[BnOH] 0:[ε-CL] 0=1:0:300.Polymerization reaction starts to carry out.Except volume Outside external declaration, the total volume of polymerization reaction passes through the amount control for adjusting solvent toluene in 3.44ml.30 DEG C of reaction temperature of control, 90min is reacted, distilled water is added and terminates reaction, reaction solution is poured into n-hexane and staticly settled, and is filtered, by filtrate methylene chloride Dissolution is added appropriate n-hexane and solid is precipitated, repeatedly three times after, filtering is drained, and vacuum drying obtains polycaprolactone.Conversion Rate: 100%, number-average molecular weight Mn=1.58 × 103g/mol, molecular weight distribution D=1.24.
Embodiment 8
Zinc catalyst Zn1 (10.2mg, 0.02mmol) is added in Schlenk bottles under nitrogen protection, 1.58ml was purified Solvent toluene, 1ml lithium methide (toluene solution of MeLi, 0.08mol/L), make [Zn1] 0/ [MeLi] 0=1/4 (molar ratio, Similarly hereinafter), after reacting 2h at room temperature, the Bian alcohol (toluene solution of BnOH, 0.1mol/L) and 0.66ml of 0.2ml are added with syringe ε-CL, make [Zn1] 0=0.0058M, [Zn1] 0:[BnOH] 0:[ε-CL] 0=1:1:300.Polymerization reaction starts to carry out.It removes Outside additional description, the total volume of polymerization reaction passes through the amount control for adjusting solvent toluene in 3.44ml.Control reaction temperature 30 DEG C, 30min is reacted, distilled water is added and terminates reaction, reaction solution is poured into n-hexane and staticly settled, and is filtered, by filtrate dichloro Methane dissolution is added appropriate n-hexane and solid is precipitated, repeatedly three times after, filtering is drained, and vacuum drying obtains polycaprolactone. Conversion ratio: 100%, number-average molecular weight Mn=11.2 × 103g/mol, molecular weight distribution D=1.14.
Embodiment 9
Zinc catalyst Zn1 (10.2mg, 0.02mmol) is added in Schlenk bottles under nitrogen protection, 1.36ml was purified Solvent toluene, 1ml lithium methide (toluene solution of MeLi, 0.08mol/L), make [Zn1] 0/ [MeLi] 0=1/4 (molar ratio, Similarly hereinafter), after reacting 2h at room temperature, the Bian alcohol (toluene solution of BnOH, 0.1mol/L) and 0.88ml of 0.2ml are added with syringe ε-CL, make [Zn1] 0=0.0058M, [Zn1] 0:[BnOH] 0:[ε-CL] 0=1:1:400.Polymerization reaction starts to carry out.It removes Outside additional description, the total volume of polymerization reaction passes through the amount control for adjusting solvent toluene in 3.44ml.Control reaction temperature 30 DEG C, 10min is reacted, distilled water is added and terminates reaction, reaction solution is poured into n-hexane and staticly settled, and is filtered, by filtrate dichloro Methane dissolution is added appropriate n-hexane and solid is precipitated, repeatedly three times after, filtering is drained, and vacuum drying obtains polycaprolactone. Conversion ratio: 98.5%, number-average molecular weight Mn=17.7 × 103g/mol, molecular weight distribution D=1.11.
Embodiment 10
Zinc catalyst Zn1 (10.2mg, 0.02mmol) is added in Schlenk bottles under nitrogen protection, 1.14ml was purified Solvent toluene, 1ml lithium methide (toluene solution of MeLi, 0.08mol/L), make [Zn5] 0/ [MeLi] 0=1/4 (molar ratio, Similarly hereinafter), after reacting 2h at room temperature, the Bian alcohol (toluene solution of BnOH, 0.1mol/L) and 1.1ml of 0.2ml are added with syringe ε-CL, make [Zn1] 0=0.0058M, [Zn1] 0:[BnOH] 0:[ε-CL] 0=1:1:500.Polymerization reaction starts to carry out.It removes Outside additional description, the total volume of polymerization reaction passes through the amount control for adjusting solvent toluene in 3.44ml.Control reaction temperature 30 DEG C, 10min is reacted, distilled water is added and terminates reaction, reaction solution is poured into n-hexane and staticly settled, and is filtered, by filtrate dichloro Methane dissolution is added appropriate n-hexane and solid is precipitated, repeatedly three times after, filtering is drained, and vacuum drying obtains polycaprolactone. Conversion ratio: 98.5%, number-average molecular weight Mn=20.7 × 103g/mol, molecular weight distribution D=1.17.
Embodiment 11
Zinc catalyst Zn1 (10.2mg, 0.02mmol) is added in Schlenk bottles under nitrogen protection, 0.04ml was purified Solvent toluene, 1ml lithium methide (toluene solution of MeLi, 0.08mol/L), make [Zn5] 0/ [MeLi] 0=1/4 (molar ratio, Similarly hereinafter), after reacting 2h at room temperature, the Bian alcohol (toluene solution of BnOH, 0.1mol/L) and 2.2ml of 0.2ml are added with syringe ε-CL, make [Zn1] 0=0.0058M, [Zn1] 0:[BnOH] 0:[ε-CL] 0=1:1:1000.Polymerization reaction starts to carry out.It removes Outside additional description, the total volume of polymerization reaction passes through the amount control for adjusting solvent toluene in 3.44ml.Control reaction temperature 30 DEG C, 3min is reacted, distilled water is added and terminates reaction, reaction solution is poured into n-hexane and staticly settled, and is filtered, by filtrate dichloromethane Alkane dissolution is added appropriate n-hexane and solid is precipitated, repeatedly three times after, filtering is drained, and vacuum drying obtains polycaprolactone.Turn Rate: 100%, number-average molecular weight Mn=59.2 × 103g/mol, molecular weight distribution D=1.58.
Embodiment 12
Zinc catalyst Zn2 (11.1mg, 0.02mmol) is added in Schlenk bottles under nitrogen protection, 2ml was purified molten Agent toluene, 1ml lithium methide (toluene solution of MeLi, 0.08mol/L), make [Zn2] 0/ [MeLi] 0=1/4 (molar ratio, under Together), after reacting 2h at room temperature, the ε-CL of 0.44ml is added with syringe, makes [Zn2] 0=0.0058M, [Zn2] 0:[BnOH] 0: [ε-CL] 0=1:0:200.Polymerization reaction starts to carry out.In addition to additional description, the total volume of polymerization reaction passes through adjusting solvent The amount of toluene is controlled in 3.44ml.3min is reacted in 30 DEG C of reaction temperature of control, and distilled water is added and terminates reaction, reaction solution pours into It is staticly settled in n-hexane, filters, filtrate is dissolved with methylene chloride, appropriate n-hexane is added, solid is precipitated, repeatedly three After secondary, filtering is drained, and vacuum drying obtains polycaprolactone.Conversion ratio: 100%, number-average molecular weight Mn=21.0 × 103g/mol, Molecular weight distribution D=1.47.
Embodiment 13
Zinc catalyst Zn2 (11.1mg, 0.02mmol) is added in Schlenk bottles under nitrogen protection, 1.78ml was purified Solvent toluene, 1ml lithium methide (toluene solution of MeLi, 0.08mol/L), make [Zn2] 0/ [MeLi] 0=1/4 (molar ratio, Similarly hereinafter), after reacting 2h at room temperature, the ε-CL of 0.66ml is added with syringe, makes [Zn2] 0=0.0058M, [Zn2] 0:[BnOH] 0:[ε-CL] 0=1:0:300.Polymerization reaction starts to carry out.In addition to additional description, it is molten that the total volume of polymerization reaction passes through adjusting The amount of agent toluene is controlled in 3.44ml.3min is reacted in 30 DEG C of reaction temperature of control, and distilled water is added and terminates reaction, reaction solution falls Enter in n-hexane and staticly settle, filter, filtrate is dissolved with methylene chloride, appropriate n-hexane is added, solid is precipitated, repeatedly After three times, filtering is drained, and vacuum drying obtains polycaprolactone.Conversion ratio: 100%, number-average molecular weight Mn=23.4 × 103g/ Mol, molecular weight distribution D=1.27.
Embodiment 14
Zinc catalyst Zn2 (11.1mg, 0.02mmol) is added in Schlenk bottles under nitrogen protection, 1.34ml was purified Solvent toluene, 1ml lithium methide (toluene solution of MeLi, 0.08mol/L), make [Zn2] 0/ [MeLi] 0=1/4 (molar ratio, Similarly hereinafter), after reacting 2h at room temperature, the ε-CL of 1.1ml is added with syringe, makes [Zn2] 0=0.0058M, [Zn2] 0:[BnOH] 0:[ε-CL] 0=1:0:500.Polymerization reaction starts to carry out.In addition to additional description, it is molten that the total volume of polymerization reaction passes through adjusting The amount of agent toluene is controlled in 3.44ml.3min is reacted in 30 DEG C of reaction temperature of control, and distilled water is added and terminates reaction, reaction solution falls Enter in n-hexane and staticly settle, filter, filtrate is dissolved with methylene chloride, appropriate n-hexane is added, solid is precipitated, repeatedly After three times, filtering is drained, and vacuum drying obtains polycaprolactone.Conversion ratio: 100%, number-average molecular weight Mn=26.8 × 103g/ Mol, molecular weight distribution D=1.65.
Embodiment 15
Zinc catalyst Zn2 (11.1mg, 0.02mmol) is added in Schlenk bottles under nitrogen protection, 2ml was purified molten Agent toluene, 1ml lithium methide (toluene solution of MeLi, 0.08mol/L), make [Zn2] 0/ [MeLi] 0=1/4 (molar ratio, under Together), after reacting 2h at room temperature, the ε-CL of 0.44ml is added with syringe, polymerization reaction starts to carry out.Control reaction temperature 30 DEG C, 3min is reacted, is further continued for that the ε-CL of 0.66ml is added with syringe, distilled water termination reaction, reaction is added after reacting 3min Liquid is poured into n-hexane and is staticly settled, and filtering dissolves filtrate with methylene chloride, appropriate n-hexane is added, solid is precipitated, so After repeatedly for three times, filtering is drained, and vacuum drying obtains polycaprolactone.Conversion ratio: 100%, number-average molecular weight Mn=30.0 × 103g/mol, molecular weight distribution D=1.51.
Above-described embodiment is used to illustrate the present invention, rather than limits the invention, in spirit of the invention and In scope of protection of the claims, to any modifications and changes that the present invention makes, protection scope of the present invention is both fallen within.

Claims (9)

1. a kind of Zn complex containing double Amino-phenoxv ligands, it is characterised in that have following structural formula:
R in the above structure1、R2And R3Be each independently selected from the alkyl or aryl of C1~C10 straight chain, branched structure, hydrogen atom or Halogen atom；X is selected from halogen atom or acetate ion.
2. the Zn complex according to claim 1 containing double Amino-phenoxv ligands, which is characterized in that in the structure R1 is selected from hydrogen atom, methyl, tert-butyl, chlorine atom, bromine atom or iodine atom, and R2 and R3 are selected from alkyl or phenyl, and R2 and R3 can With identical or different；X is selected in chlorine atom, bromine atom or acetate ion.
3. a kind of purposes of Zn complex described in claim 1, which is characterized in that it is applied to ring-opening polymerization of lactone by catalysis, it is interior Ester is lactide, glycolide, butyrolactone, valerolactone, caprolactone, heptalactone, caprylolactone.
4. application according to claim 3, which is characterized in that using Zn complex described in claim 1 as catalyst, with Internal ester monomer carries out ring-opening polymerization and generates polymer, the application specifically: by the Zn complex alkane with 4 equivalents in a solvent The mixing of base lithium, reaction is allowed to in-situ preparation alkyl Zn complex, under conditions of alcohol is not added, internal ester monomer is added and polymerize instead It answers；The solvent is by one of benzene, toluene, tetrahydrofuran, methylene chloride or a variety of forms；Catalyst and lactone when polymerization Molar ratio is 1:50~10000；The temperature range of polymerization reaction is 0~120 DEG C, and polymerization time is 3 minutes to 3 hours.
5. application according to claim 3, which is characterized in that using Zn complex described in claim 1 as catalyst, with Internal ester monomer carries out ring-opening polymerization and generates polymer, the application specifically: by the Zn complex alkane with 4 equivalents in a solvent The mixing of base lithium, reaction are allowed to in-situ preparation alkyl Zn complex, and under conditions of alcohol is added as initiator, internal ester monomer is added Carry out polymerization reaction；The solvent is by one of benzene, toluene, tetrahydrofuran, methylene chloride or a variety of forms；It is catalyzed when polymerization The molar ratio of agent and alcohol and lactone is 1:0~10:50~10000；The alcohol is C1~C10 straight chain, branch or cyclic annular knot The alkylol or benzylalcohol of structure, the temperature range of polymerization reaction are 0~120 DEG C, and polymerization time is 3 minutes to 3 hours.
6. application according to claim 5, which is characterized in that the initiator is benzylalcohol.
7. application according to claim 4 or 5, which is characterized in that the solvent is toluene.
8. application according to claim 4 or 5, which is characterized in that the polymeric reaction temperature is 30 DEG C.
9. according to right want 4 or 5 described in application, which is characterized in that the range of number-average molecular weight of the polymer 1000~ Within 15000gmol-1, molecular weight distribution D < 1.6.
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