CN105968332A - Benzoborazole metal complex for catalyzing cyclic ester polymerization and application thereof - Google Patents
Benzoborazole metal complex for catalyzing cyclic ester polymerization and application thereof Download PDFInfo
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- 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
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- 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
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Abstract
The invention discloses a benzoborazole metal complex for catalyzing cyclic ester polymerization and application thereof, relates to the technical field of organic chemistry catalysis and particularly relates to a metal catalyst coordinated with benzoborazole. The benzoborazole metal complex is a compound with a structure shown in the formula (I). The complex disclosed by the invention is used for catalyzing cyclic ester polymerization. Compared with the traditional tin catalyst, the catalyst disclosed by the invention has very high catalytic activity, namely that benzoborazole metal complex has strong catalytic activity in body polymerization and solution polymerization, and the product of catalytic polymerization has the characteristic of narrow molecular weight distribution.
Description
Technical field
The present invention relates to organic chemistry catalysis technical field, particularly relate to a kind of and the coordination of benzo borazol metal catalytic
Agent.
Background technology
Under the situation serious in environmental problem, petroleum resources are short, biodegradable plastic has obtained paying close attention to widely.Due to
Its good biological degradability, biocompatibility and hypotoxicity, aliphatic polyester is just becoming Biodegradable material area research
Focus.Wherein, the polycaprolactone (PCL) having huge applications prospect in terms of organizational project and medicine controlled release carrier is subject to especially
A lot of concerns.PCL is as far back as the thirties in last century, by the Carothers et al. the ring-opening polymerisation by 6-caprolactone (ε-CL)
Reaction (Ring-opening polymerization, ROP) prepares.Polycaprolactone is hydrophobicity, semi-crystalline polymer,
Its degree of crystallinity can be degraded along with polymer molecule Quality Down, polymer under microbial action.It is mainly used in view of PCL
Medical science and pharmaceutics, therefore, the effective ROP catalyst system and catalyzing preparing PCL is always important research direction.
Distinguishing with ring-opening polymerization mechanism, the catalyst being applied to cyclic esters ring-opening polymerization includes following coordination-insertion mechanism
Metallic catalyst and by activated monomer or the organic catalyst of initiator.Wherein meet the stannum (Sn) of coordination-insertion mechanism
Metalloid salt divided ring polymerization is prepared the industrialization of polyester and is had tremendous influence.Stannum class is urged by the Kricheldorf etc. of Germany
Change mechanism to conduct in-depth research, relate to the tin catalyst mechanism of action to multiple cyclic ester monomer, including lactide, in oneself
Ester, trimethylene carbonate etc. (Polymer, 1995,36 (6): 1253-1259.).Kricheldorf etc. think stannum metalloid
The catalysis activity of salt comes from metal center sky sp3d2Track: at dibutyl two isooctyl acid stannum (Bu2SnOct2In), metal center
There are two empty sp3d2Track, octanoic acid group is weakened by steric effect as dentate, reactivity；And stannous iso caprylate
(SnOct2) there are three empty sp3d2Track, lewis acid acidity is higher, and catalysis activity is higher, is more suitably applied to industry metaplasia
Produce (Macromolecules, 1988,21 (2): 286-293.).Comparatively speaking, the organic catalyst of difference activation mechanism is utilized
Controlling extent embodies advantage, but not as good as conventional metals salt in catalysis activity.
At present, be applied to lactone coordination ring-opening polymerisation catalyst system mainly include stannous octoate, metallic aluminium, calcium, magnesium,
Zinc, titanium family complex and IIIB metal complex etc..Ring-opening polymerisation is prepared in the catalyst of polycaprolactone, the most pungent
Acid stannous, the alcohol of small-molecular-weight can control polymer molecular weight and molecular weight distribution as (being total to) initiator.But, above-mentioned urge
Agent system or activity is higher but molecular weight of product distribution width, or narrow molecular weight distribution but activity is low, be all difficult to take into account work
Property high the and feature of narrow molecular weight distribution.
Boric acid application in terms of catalysis is quite extensive, from basis organic reaction, to the structure of carbon skeleton, lacking of boranes
Electronic Keying, for regulation and control substrate group electronics distribution, has remarkable effect.Benkovic etc. find, in borazol building-up process, from
Raw material is to product, and centered by boron atom, boron oxygen key or other hetero atoms being connected with borine are respectively provided with extremely strong electrophilic
Ability (J.Am.Chem.Soc.2013,135:14544-14547).This enlightens us and utilizes strong electrophilic part, strengthens metal
The electrophilic ability at center, thus activate lactone carbonyl oxygen atom.
Summary of the invention
In view of prior art exists above-mentioned technical problem, the invention provides a kind of benzo borazol being catalyzed cyclic ester polymerization
Metal complex and application thereof, this metal complex belongs to borazol metal complex, and it can the opening of efficient catalytic 6-caprolactone
Cyclopolymerization, has high catalytic activity, and obtains the polycaprolactone product that molecular weight distribution is narrower.
Benzo borazol metal complex of the present invention have employed following technical scheme.
The present invention provides a kind of benzo borazol metal complex being catalyzed cyclic ester polymerization, described benzo borazol metal combination
Thing is the compound with formula (I) structure:
Wherein, R1、R2、R3、R4In, at least include 3 hydrogen atoms；Work as R1、R2、R3、R4When being not hydrogen atom respectively, R1、
R2、R3、R4C can be elected independently of one another as1-C12Chain alkyl, C3-C8Cycloalkyl group, C2-C8Alkylene, C2-C5's
Alkynes base, fluorine atom, chlorine atom, bromine atoms,R8、R9Elect C independently of one another as1-C5Alkane
Alkyl, C1-C5Alkoxyl or hydrogen atom；
R5For hydrogen atom orR6、R7In, at least include 1 hydrogen atom, work as R6、R7It is not that hydrogen is former respectively
The period of the day from 11 p.m. to 1 a.m, R6、R7It is chosen as C1-C12Chain alkyl, C3-C8Cycloalkyl group, C2-C8Alkylene, C2-C5Alkynes base, fluorine
Atom, chlorine atom, bromine atoms, nitro, benzyloxy；M is Sn or Zn, preferably Sn.
Preferably described R1、R2、R3、R4In, at least include 3 hydrogen atoms；Work as R1、R2、R3、R4When being not hydrogen atom respectively,
R1、R2、R3、R4C can be elected independently of one another as1-C6Linear paraffin base, C3-C8Branched alkane alkyl, C3-C6Cycloalkyl group,
Fluorine atom, chlorine atom, bromine atoms, phenyl, benzyl；
The structure that concrete described benzo borazol metal complex is as shown in table 1:
Table 1
R5For hydrogen atom orWherein, R6、R7In, at least include 1 hydrogen atom, work as R6、R7The most not
During for hydrogen atom, R6、R7It is chosen as C1-C4Linear paraffin base, fluorine atom；M is Sn or Zn.
Described benzo borazol metal complex is applied to the ring-opening polymerisation of cyclic ester structural compounds.
The method synthesizing described benzo borazol metal complex is:
With 1,2-oxygen bora Pentamethylene. or 2-chloro-1,2-oxygen bora Pentamethylene. is boron ring raw material, with hexichol acyl chlorides for replacing
The raw material of phenyl, boron ring raw material and phenyl material dissolution, in DMF, be heated to 60 DEG C, adds paraformaldehyde as carbonyl material,
React after clarifying to system, add the aromatic derivant of ethylenediamine, or after adding fluorine benzimidazole dihydrochloride, calcium chloride and phenol reactant
Add the aromatic derivant of ethylenediamine, after blending reaction, be slowly added dropwise stannous chloride or zinc chloride to system, separate out white powder
End, filter after thick product, column chromatography purification obtains described benzo borazol metal complex.
The method of catalysis cyclic ester polymerization reaction is:
By cyclic ester monomer, benzo borazol metal complex and coinitiator, heating, isothermal reaction；
Or by cyclic ester monomer, dissolve with organic solvent, add benzo borazol metal complex and coinitiator, room temperature is anti-
Should.
Described coinitiator, for MeOH, EtOH,nPrOH、1PrOH、nBuOH、tBuOH、BnOH、Ph2CHOH、Ph3COH、Ph
(CH2OH)3、N(CH2CH2OH)3In one or more.Above-mentioned alcohol and described benzo borazol metal complex mol ratio can be
Change in the biggest scope: (0.1-10): 1.The molecular weight of polymer can be controlled with coordination compound mol ratio by above-mentioned alcohol,
In the range of 0.1 ten thousand-20 ten thousand, accurate scalable, molecular weight distribution are between 1.01-1.20, active polymerization feature.
Stable smelting process is also included, stablizing in smelting process in the application of described benzo borazol metal complex
Agent is trialkyl phosphorous acid, is obstructed in cyclic nonaromatics, the space are obstructed in alkyl phosphorous acid, aromatic series phosphorous acid, space
Diphosphorous acid compound, hydroxy phenylpropionic acid, hvdroxvbenzvl compounds, benzyl alcohol, alkylidene bisphenols, alkyl phenol, aminoacid, sulfur
One or more mixture in the amino-compound that is obstructed in ether, space, hydroquinone.
In the application of described benzo borazol metal complex, also include stable smelting process, in smelting process except water
Agent is in clay, aluminium oxide, silica gel, zeolite, calcium chloride, calcium carbonate, sodium sulfate, calcium bicarbonate, sodium bicarbonate, potassium bicarbonate
One or more mixture.Be obstructed (alkyl, aryl, phenolic group) hydrazides, aromatic series or aliphatic can also be added in polymerization inhibitor
Amide mono hydroxyeicosatetraenoic acid or dihydroxy acid, cyclic amides, aliphatic or aromatic hydrazone aldehyde or dihydrazone aldehyde, diacyl-hydrazides derive
Thing.
Described benzo borazol metal complex, except preparing polycaprolactone, it is also possible to having in smelting process
Machine solvent is prepared polycaprolactone, described organic solvent be benzene,toluene,xylene, DMF, chloroform,
One in dichloromethane, acetonitrile, pyridine, dimethyl sulfoxide, Isosorbide-5-Nitrae-dioxane, furan, oxolane.Reaction mixture can be
Another kind of polar solvent separates out pressed powder.
Heretofore described cyclic ester structure be selected from the one having in the cyclic compound monomer of formula (III) structure or
Several:
Wherein, A is [-(CR8R9)-]；R8、R9Selected from H, there is the alkyl of 1～5 carbon atom and to have 1～5 carbon former
Identical or different group in alkyl that is sub and that replaced by halogen atom or hydroxyl；X is selected from O or N；Or selected from having formula (IV)
One or more in the cyclic compound monomer of structure:
Wherein, A, B are [-(CR10R11)-]n, n is the integer of 2～6, A and B can be the same or different；R10、R11Choosing
From H, there is 1～5 carbon atom alkyl, there is 1～5 carbon atom the alkyl replaced by halogen atom or hydroxyl；X is selected from O
Or NH.
Beneficial effect:
The invention provides a kind of borazol metal complex catalysts, this catalyst is compared tradition tin catalyst and is had high
Catalysis activity, no matter i.e. described benzo borazol metal complex all embodies in polymerisation in bulk or polymerisation in solution is urged by force
Change activity, and the product of catalytic polymerization has the feature of narrow molecular weight distribution.
1, boracic slaine is used for the ring-opening polymerisation of cyclic ester by the present invention first；
2, benzo borazol metal complex of the present invention has high catalytic activity to 6-caprolactone, and its activity is higher than mesh
Front had been reported that in traditional pink salt and organic catalyst；
3, the metal complex catalyzed 6-caprolactone of benzo borazol of the present invention and other lactones and lactide monomers are used
The molecular weight of product narrow distribution of polymerization, and can be with Molecular regulator amount size, active polymerization feature.
Detailed description of the invention
In order to further illustrate the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but
These describe simply as further illustrating the features and advantages of the present invention rather than limiting to the claimed invention.
Synthetic method (Compound numbers represents structure in nuclear magnetic data table)
Compound 1: by 1,2-oxygen bora Pentamethylene. (2.212g), hexichol acyl chlorides (1.785g) are dissolved in DMF (100mL)
In, it is slowly added to paraformaldehyde (1.236g) at oil bath 60 DEG C, reacts at 60 DEG C to system clarification.Add N, N '-bis-(phenyl Asias
Methyl)-1，2-diaminoethane (3.235g), after at room temperature reacting 6 hours, the DMF being slowly added dropwise stannous chloride (4.226g) is molten
Liquid, continues reaction 2 hours after separating out white solid to system.After reaction terminates, stand and filter, decompressing and extracting solvent, obtain
Crude product carries out column chromatography for separation (petroleum ether/dichloromethane burns=1/4) and obtains yellow product, productivity 82.2%.
Compound 2: by 1,2-oxygen bora Pentamethylene. (2.212g), hexichol acyl chlorides (1.785g) are dissolved in DMF (100mL)
In, it is slowly added to paraformaldehyde (1.236g) at oil bath 60 DEG C, reacts at 60 DEG C to system clarification.Add N, N '-bis-(phenyl Asias
Methyl)-1，2-diaminoethane (3.235g), after at room temperature reacting 6 hours, the DMF being slowly added dropwise protochloride zinc (3.656g) is molten
Liquid, continues reaction 2 hours after separating out white solid to system.After reaction terminates, stand and filter, decompressing and extracting solvent, obtain
Crude product carries out column chromatography for separation (petroleum ether/dichloromethane burns=1/5) and obtains yellow product, productivity 73.5%.
Compound 3: by chloro-for 2-1,2-oxygen bora Pentamethylene. (3.011g), hexichol acyl chlorides (1.785g) are dissolved in DMF
(100mL) in, at oil bath 60 DEG C, it is slowly added to paraformaldehyde (1.236g), reacts at 100 DEG C to system clarification.Add benzenesulfonic acid
(4.252g) acetonitrile solution and calcium chloride (0.5g), stirring to system is emulsus, static, filtration.In filtrate add N, N '-
Double (phenylmethylene)-1，2-diaminoethane (3.235g), after at room temperature reacting 8 hours, are slowly added dropwise stannous chloride
(4.226g) DMF solution, continues reaction 2 hours after separating out white solid to system.After reaction terminates, stand and filter, decompression
Draining solvent, the crude product obtained carries out column chromatography for separation (petroleum ether/dichloromethane burns=1/4) and obtains yellow product, productivity
74.8%.
Compound 4: by chloro-for 2-1,2-oxygen bora Pentamethylene. (3.011g), hexichol acyl chlorides (1.785g) are dissolved in DMF
(100mL) in, being slowly added to paraformaldehyde (1.236g) at oil bath 60 DEG C, react and clarify to system at 60 DEG C, system is taken out repeatedly
Vacuum three times.Adding acetonitrile solution, calcium chloride (0.5g) and the phenol (3.122g) of fluorine benzimidazole dihydrochloride (3.122g), stirring is to system
In emulsus, static, filtration.Add N, N '-bis-(phenylmethylene)-1，2-diaminoethane (3.235g), react 24 hours at 45 DEG C
After, it is slowly added dropwise the DMF solution of stannous chloride (4.226g), after separating out white solid to system, continues reaction 2 hours.Reaction knot
Shu Hou, stands and filters, decompressing and extracting solvent, and the crude product obtained carries out column chromatography for separation (n-hexane/ethyl acetate=4/1) and obtains
To white powder, productivity 82.2%.
Compound 5: by chloro-for 2-1,2-oxygen bora Pentamethylene. (3.011g), hexichol acyl chlorides (1.785g) are dissolved in DMF
(100mL) in, being slowly added to paraformaldehyde (1.236g) at oil bath 60 DEG C, react and clarify to system at 60 DEG C, system is taken out repeatedly
Vacuum three times.Adding acetonitrile solution, calcium chloride (0.5g) and the benzoyl chloride (3.211g) of fluorine benzimidazole dihydrochloride (3.122g), stirring is to body
It is in emulsus, static, filtration.Filtrate adds N, N '-bis-(phenylmethylene)-1，2-diaminoethane (3.235g), at room temperature stirs
After mixing reaction 6 hours, it is slowly added dropwise the DMF solution of stannous chloride (4.226g), after separating out white solid to system, continues reaction 2
Hour.After reaction terminates, standing and filter, decompressing and extracting solvent, the crude product obtained carries out column chromatography for separation (petroleum ether/dichloro
First burns=1/1) obtain yellow product, productivity 81.6%.
Nuclear magnetic data table (300MHz, CDCl3):
Embodiment 1-5
Embodiment 1-5 have employed different metal complexs as catalyst, carries out body under identical reaction conditions
Polymerization.The 6-caprolactone being respectively 5.7g (50mmol) is respectively placed in 50mL flask, adds 0.1mmol metal complex,
0.1mmol benzyl alcohol.Oil bath heating at 120 DEG C.Isothermal reaction 15min, cooling, sample analysis, use liquid chromatogram measuring to turn
Rate, uses GPC to measure molecular weight (polystyrene is standard specimen).The experimental result of embodiment 1-10 is shown in Table 1.
The monomer of the 6-caprolactone described in embodiment 1-5 is the product that in caprolactone production process, after rectification, purity is higher
Product.
Bulk polymerization under table 1 different catalysts effect
Embodiment 6-10
Embodiment 6-10 uses the metal complex in above-described embodiment 4 as catalyst, enters under condition of different temperatures
Row polymerisation in bulk.Respectively the 6-caprolactone of 5.7g (50mmol) is respectively placed in 50mL flask, adds in 0.1mmol embodiment 1
Metal complex, 0.1mmol benzyl alcohol.Oil bath heating at a temperature of 5 kinds, isothermal reaction 15min, cooling, sample analysis, use liquid
Phase chromatographic determination conversion ratio, uses GPC to measure molecular weight (polystyrene is standard specimen).The experimental result of embodiment 11-15 is shown in Table
2。
The monomer of the 6-caprolactone described in embodiment 6-10 is the product that in caprolactone production process, after rectification, purity is higher
Product.
Polymerization result under table 2 different temperatures
Embodiment 11-16
In embodiment 11-16, the metal complex in employing above-described embodiment 4 is as catalyst, at different catalysts consumption
Under the conditions of carry out polymerisation in bulk.Respectively the 6-caprolactone of 5.7g (50mm01) is respectively placed in 50mL flask, adds in embodiment 2
5 batch quality of metal complex, 0.1mmol benzyl alcohol.Oil bath heating at 120 DEG C.Isothermal reaction 20min, cooling, sampling
Analyzing, conversion ratio records with liquid chromatograph, and molecular weight records (polystyrene is as standard specimen) with GPC.The experiment knot of embodiment 11-16
Fruit is shown in Table 3.
The monomer of the 6-caprolactone described in embodiment 11-16 is the product that in caprolactone production process, after rectification, purity is higher
Product.
The impact on aggregate rate of the table 3 metal complex different amounts
Embodiment 17-26
In embodiment 17-26, the metal complex in employing above-described embodiment 1 is as catalyst, at different organic solvents bar
Polymerisation in solution is carried out under part.Respectively the 6-caprolactone of 5.7g (50mmol) is respectively placed in 50mL flask, adds different organic molten
Agent 15mL.Add metal complex 0.5mmol in embodiment 4,0.5mmol benzyl alcohol.Room temperature isothermal reaction 1 hour, sampling point
Analysis, conversion ratio records with liquid chromatograph, and end-product pours precipitation white solid in ice methanol into, and molecular weight records (polyphenyl second with GPC
Alkene is standard specimen).The experimental result of embodiment 17-26 is shown in Table 4.
The monomer of the 6-caprolactone described in embodiment 17-26 is the product that in caprolactone production process, after rectification, purity is higher
Product.
Table 4: be polymerized situation in different organic solvents
Embodiment 27-30
Embodiment 27-30 uses the metal complex of above-described embodiment 9 as catalyst, is catalyzed 4 kinds of different cyclic esters and enters
Row polymerisation in bulk.Respectively by 4 kinds, the cyclic ester of 5g is respectively placed in 50mL flask, adds polymerization inhibitor in 1mg embodiment 3, at 120 DEG C
Oil bath is heated, and reacts 4 hours, cooling, the content of sample analysis cyclic ester.Cyclic ester conversion ratio (i.e. aggregate rate) is calculated with this, real
The experimental result executing example 27-30 is shown in Table 5.
The polymerization of the different cyclic ester monomer of table 5
Claims (8)
1. the benzo borazol metal complex being catalyzed cyclic ester polymerization, it is characterised in that described benzo borazol metal combination
Thing is the compound with the structure shown in formula (I):
Wherein, R1、R2、R3、R4In, at least include 3I hydrogen atom；Work as R1、R2、R3、R4When being not hydrogen atom respectively, R1、R2、R3、
R4C can be elected independently of one another as1-C12Chain alkyl, C3-C8Cycloalkyl group, C2-C8Alkylene, C2-C5Alkynes
Base, fluorine atom, chlorine atom, bromine atoms,OrR8、R9Elect C independently of one another as1-C5Alkane
Base, C1-C5Alkoxyl or hydrogen atom；
R5For hydrogen atom orR6、R7In, at least include 1 hydrogen atom, work as R6、R7When being not hydrogen atom respectively,
R6、R7It is chosen as C1-C12Chain alkyl, C3-C8Cycloalkyl group, C2-C8Alkylene, C2-C5Alkynes base, fluorine atom,
Chlorine atom, bromine atoms, nitro, benzyloxy；M is Sn or Zn.
Benzo borazol metal complex the most according to claim 1, it is characterised in that described R1、R2、R3、R4In, at least
Including 3 hydrogen atoms；Work as R1、R2、R3、R4When being not hydrogen atom respectively, R1、R2、R3、R4C can be elected independently of one another as1-C6Straight
Alkenyl group, C3-C8Branched alkane alkyl, C3-C6Cycloalkyl group, fluorine atom, chlorine atom, bromine atoms, benzene IV base, benzyl；
R5For hydrogen atom orWherein, R6、R7In, at least include 1 hydrogen atom, work as R6、R7It is not that hydrogen is former respectively
The period of the day from 11 p.m. to 1 a.m, R6、R7It is chosen as C1-C4Linear paraffin base, fluorine atom；M is Sn or Zn.
Benzo borazol metal complex the most according to claim 1 and 2, it is characterised in that described benzo borazol metal
The structure that coordination compound is as shown in table 1:
Table 1
。
4. answering according to the benzo borazol metal complex being catalyzed cyclic ester polymerization described in claims 1 to 3 any one
With, it is characterised in that described benzo borazol metal complex is applied to the ring-opening polymerisation of cyclic ester structural compounds.
Application the most according to claim 4, it is characterised in that the method for catalysis cyclic ester polymerization reaction is:
By cyclic ester monomer, benzo borazol metal complex and coinitiator, heating, isothermal reaction；
Or by cyclic ester monomer, dissolve with organic solvent, add benzo borazol metal complex and coinitiator, room temperature reaction.
Application the most according to claim 5, it is characterised in that described cyclic ester monomer is selected from having formula III structure
One or more in cyclic compound monomer:
Wherein, A is [-(CR8R9)-]；R8、R9Selected from H, there is the alkyl of 1～5 carbon atom and there is 1～5 carbon atom also
Identical or different group in the alkyl replaced by halogen atom or hydroxyl；X is selected from O or N；Or selected from having formula (IV) structure
Cyclic compound monomer in one or more:
Wherein, A, B are [-(CR10R11)-]n, n is the integer of 2～6, A and B can be the same or different；R10、R11Selected from H,
There is the alkyl of 1～5 carbon atom, there is 1～5 carbon atom the alkyl replaced by halogen atom or hydroxyl；X is selected from O or NH.
Application the most according to claim 5, it is characterised in that described coinitiator is MeOH, EtOH,nPrOH、iPrOH、 nBuOH、tBuOH、BnOH、Ph2CHOH、Ph3COH、Ph(CH2OH)3、N(CH2CH2OH)3In one.
Application the most according to claim 5, it is characterised in that described organic solvent is benzene,toluene,xylene, N, N-
One in dimethylformamide, chloroform, dichloromethane, acetonitrile, pyridine, dimethyl sulfoxide, Isosorbide-5-Nitrae-dioxane, furan,
Oxolane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106083906A (en) * | 2016-07-12 | 2016-11-09 | 安徽红太阳新材料有限公司 | The miaow borazol metal complex of catalysis cyclic ester polymerization and application thereof |
| CN114644645A (en) * | 2022-03-08 | 2022-06-21 | 南京农业大学 | 3-indole-substituted phenylborozole compound and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104105736A (en) * | 2011-12-16 | 2014-10-15 | 沙特基础工业公司 | Process for synthesizing a new catalyst complex for the production of polyethylene terephthlate |
| CN105061501A (en) * | 2015-08-07 | 2015-11-18 | 江苏红太阳新材料有限公司 | Metal complex for catalyzing cycloate polymerization and application of metal complex for catalyzing cycloate polymerization |
| CN105348495A (en) * | 2015-11-22 | 2016-02-24 | 云南民族大学 | Catalyst for polylactone preparation |
| CN106083906A (en) * | 2016-07-12 | 2016-11-09 | 安徽红太阳新材料有限公司 | The miaow borazol metal complex of catalysis cyclic ester polymerization and application thereof |
-
2016
- 2016-07-12 CN CN201610546838.XA patent/CN105968332A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104105736A (en) * | 2011-12-16 | 2014-10-15 | 沙特基础工业公司 | Process for synthesizing a new catalyst complex for the production of polyethylene terephthlate |
| CN105061501A (en) * | 2015-08-07 | 2015-11-18 | 江苏红太阳新材料有限公司 | Metal complex for catalyzing cycloate polymerization and application of metal complex for catalyzing cycloate polymerization |
| CN105348495A (en) * | 2015-11-22 | 2016-02-24 | 云南民族大学 | Catalyst for polylactone preparation |
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| CN106083906A (en) * | 2016-07-12 | 2016-11-09 | 安徽红太阳新材料有限公司 | The miaow borazol metal complex of catalysis cyclic ester polymerization and application thereof |
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