CN105061501B - The metal complex for being catalyzed cyclic ester polymerization and its purposes in being catalyzed cyclic ester polymerization - Google Patents
The metal complex for being catalyzed cyclic ester polymerization and its purposes in being catalyzed cyclic ester polymerization Download PDFInfo
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- CN105061501B CN105061501B CN201510481200.8A CN201510481200A CN105061501B CN 105061501 B CN105061501 B CN 105061501B CN 201510481200 A CN201510481200 A CN 201510481200A CN 105061501 B CN105061501 B CN 105061501B
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- 0 CCC1C(C)=*(C)CCC1 Chemical compound CCC1C(C)=*(C)CCC1 0.000 description 2
- BWCBZBUCGLAPON-UHFFFAOYSA-N CCC1C2(CC(C3)C3C2)C1C Chemical compound CCC1C2(CC(C3)C3C2)C1C BWCBZBUCGLAPON-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to organic chemistry catalysis technical fields, and the metal complex for providing catalysis cyclic ester polymerization and its purposes in being catalyzed cyclic ester polymerization.The molecular formula of the metal complex isOr, wherein R1、R2、R3、R4It is respectively selected as C by oneself1–C30Chain alkyl, C3–C8Cycloalkyl group, C2–C8Alkylene, C2–C5Alkynes base,Or；R5、R6It is each independently selected from C1–C5Alkyl, C1–C5Alkoxy or hydrogen atom；M is Sn, Mg, Ca or Zn.The metal complex is suitable for the ring-opening polymerisation of cyclic ester compounds, and coinitiator can be added simultaneously.Metal complex of the present invention has high catalytic activity, and the molecular weight of product narrow distribution of polymerisation to ε caprolactones and other lactones and lactide monomers, and can adjust molecular size range, active polymerization feature.
Description
Technical field
The metal being coordinated the present invention relates to organic chemistry catalysis technical field more particularly to a kind of phosphate and pyrophosphoric acid is urged
Agent and its purposes in being catalyzed cyclic esters ring-opening polymerization.
Background technology
Under the big situation that environmental problem is serious, petroleum resources are short, biodegradable plastic has obtained extensive concern.Its
In, polycaprolactone becomes the hot topic of research and development.Polycaprolactone is hydrophobicity, semi-crystalline polymer, and crystallinity is with polymerization
Object molecular mass declines, and polymer can degrade under microbial action.The raw material of polycaprolactone industry is can be with regenerated biology
The final product of material, degradation is also all water and carbon dioxide, can with complete biodegradable, be most competitiveness can biology
One of degradable material.
The synthesis of early stage polyester is but the polymer being synthesized to be reacted with this based on the condensation reaction of acids and alcohols
Structure may be straight chain, branch or cyclic structure, and molecular weight distribution is wide, and molecular weight is low and not easy to control, thus eventually leads to
The poor mechanical property of polymer.Exploitation coordination polymerization catalysts are focused primarily upon for the study on the synthesis of polycaprolactone in recent years to draw
Hair 6-caprolactone ring-opening polymerisation prepares polycaprolactone.Compared with Direct Dehydration polycondensation method, method that ring-opening polymerisation prepares polyester
It has the following advantages：The first, the molecular weight of polyester can accurately control, and molecular weight distribution is very narrow；The second, Direct Dehydration contracts
It is low to close obtained molecular weight of polyesters, property cannot meet certain requirements in biomedicine, and anhydrous generation in ring-opening polymerisation, can
To synthesize the polymer of higher molecular weight；Third can selectively be gathered by the modification realization chiral monomer to catalyst ligand
It closes.
Currently, applied to lactone coordination ring-opening polymerisation catalyst system mainly include stannous octoate, metallic aluminium, calcium, magnesium,
Zinc, titanium family complex compound and IIIB metal complexes etc..Ring-opening polymerisation is prepared in the catalyst of polycaprolactone, most typically pungent
The alcohol of sour stannous, small-molecular-weight can be used as (total) initiator control polymer molecular weight and molecular weight distribution.But it above-mentioned urges
Either activity is higher but molecular weight of product is distributed wide or narrow molecular weight distribution but activity is low for agent system, is difficult to take into account work
The characteristics of property height and narrow molecular weight distribution.The Toyoji Kakuchi of Japan have studied the difunctional activation of phosphorus acid catalyst
Mechanism, which can effectively control in polymer molecular weight distribution and product without metal residual, but such catalyst reaction
Poor activity [Macromolecules, 2011,44 (7), 1999-2005].
It can be seen that cannot be taken into account in the catalyst of existing cyclic ester coordination ring-opening polymerisation catalytic activity and molecular weight distribution compared with
Narrow feature, and the present invention provides a kind of phosphate metal composition catalysts, the catalyst is with high catalytic activity and extensively
No matter general catalytic environment adaptability, i.e., the described metal complex embody strong catalysis in bulk polymerization or polymerisation in solution
Activity, and the product of catalytic polymerization has the characteristics that Narrow Molecular Weight Distribution.So far, this phosphate and pyrophosphoric acid are coordinated
Metallic catalyst simultaneously has not been reported.
Invention content
In view of above-mentioned technical problem exists in the prior art, the present invention provides the metal complex of catalysis cyclic ester polymerization and
Its purposes in being catalyzed cyclic ester polymerization, the metal complex belong to phosphate metal complex, being capable of efficient catalytic cyclic ester
Ring-opening polymerisation, there is high catalytic activity, and obtain the relatively narrow pla-pcl product of molecular weight distribution.Metal of the present invention is matched
It closes object and uses following technical solution.
The present invention provides the metal complex of catalysis cyclic ester polymerization, and the metal complex is the chemical combination with 1 structure of formula
Object：
Wherein, R1、R2、R3、R4It is each independently selected from C1–C30Chain alkyl, C3–C8Cycloalkyl group, C2–C8's
Alkylene, C2–C5Alkynes base,OrR5、R6It is each independently selected from C1–C5Alkyl, C1–
C5Alkoxy or hydrogen atom；M is Sn, Mg, Ca or Zn, preferably Sn or Zn.
The metal complex of the catalysis cyclic ester polymerization can also be with formula 2 in addition to the compound with 1 structure of formula
The compound of structure：
Wherein, R7、R8It is each independently selected from C1–C30Chain alkyl, C3–C8Cycloalkyl group, C2–C8Alkene
Base, C2–C5Alkynes base,OrR5、R6It is each independently selected from C1–C5Alkyl, C1–C5's
Alkoxy or hydrogen atom；M is Sn, Mg, Ca or Zn, preferably Sn or Zn.
The present invention also provides purposes of the metal complex of above-mentioned catalysis cyclic ester polymerization in being catalyzed cyclic ester polymerization, above-mentioned gold
As catalyst while coinitiator can be added in the polymerisation of cyclic ester as the catalyst to use in metal complex
Carry out the catalytic activity of intensified response.
The coinitiator, be MeOH, EtOH,nPrOH、iPrOH、nBuOH、tBuOH、BnOH、Ph2CHOH、Ph3COH、Ph
(CH2OH)3、N(CH2CH2OH)3One or more of.Above-mentioned coinitiator is with the metal complex molar ratio can be very
Change in big range such as, (0.1-10)：1.The molecular weight of polymer can be controlled by above-mentioned alcohol with complex molar ratio,
Accurate adjustable, molecular weight distribution is between 1.01-1.24 in 0.1 ten thousand-20 ten thousand ranges, active polymerization feature.
Further include stabilizer in the bulk technique of metal complex application, the stabilizer is trialkyl
Phosphorous acid, the diphosphorous acid that cyclic nonaromatics that alkyl phosphorous acid, aromatic series phosphorous acid, space are obstructed, space are obstructed
Compound, hydroxy phenylpropionic acid, hvdroxvbenzvl compounds, benzyl alcohol, alkylidene bisphenols, alkyl phenol, amino acid, thioether, space are obstructed
Amino-compound, one or more of hydroquinone mixture.
Further include deicer in the bulk technique of metal complex application, the deicer is clay, oxygen
Change one or more of aluminium, silica gel, zeolite, calcium chloride, calcium carbonate, sodium sulphate, calcium bicarbonate, sodium bicarbonate, saleratus
Mixture.Be obstructed (alkyl, aryl, phenolic group) hydrazides, aromatic series or aliphatic amide list hydroxyl can also be added in polymerization inhibitor
Sour either dihydroxy acid, cyclic amides, aliphatic or aromatic hydrazone aldehyde or dihydrazone aldehyde, diacyl-hydrazides derivative.
The metal complex can also be used in addition to that can prepare polycaprolactone in the smelting process of bulk polymerization
Solution polymerization process, prepares polycaprolactone in organic solvent, and the organic solvent is benzene,toluene,xylene, N, N- dimethyl
Formamide, chloroform, dichloromethane, acetonitrile, pyridine, dimethyl sulfoxide, one kind in 1,4- dioxanes, furans, tetrahydrochysene furan
It mutters.Solid powder can be precipitated in another polar solvent in reaction mixture.
The metal complex of above-mentioned catalysis cyclic ester polymerization is suitable for the ring-opening polymerisation of cyclic ester compounds.The cyclic ester structure
One or more of the cyclic compound monomer with 3 structure of formula can be selected from：
Wherein, A is-(CH2)5—、—(CH2)4—、—(CH2)3- or-CH2CH(CH3)CH2—；X is O；Above-mentioned ring
Ester structure can also be selected from one or more of the cyclic compound monomer with 4 structure of formula：
Wherein, A, B are [- (CR11R12)—]n, the integer that n is 2~6, A and B can be the same or different；R11、R12
Alkyl selected from H, with 1~5 carbon atom, with 1~5 carbon atom and the alkyl that is replaced by halogen atom or hydroxyl；X is selected from
O or NH.
Metal complex of the present invention has the advantages that：1, phosphate metal complex and coke for the first time of the invention
Phosphate metal complex is used for the ring-opening polymerisation of lactone as catalyst；2, metal complex of the present invention to 6-caprolactone and
Other lactones and lactide monomers have high catalytic activity；3, using metal complex catalyzed 6-caprolactone of the present invention and other
Lactone and the molecular weight of product narrow distribution of lactide monomers polymerization, and molecular size range can be adjusted, active polymerization feature.
Specific implementation mode
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are only the feature and advantage further illustrated the present invention, rather than to the claims in the present invention
Limitation.
Embodiment 1-10
Embodiment 1-10 uses different metal complexs as catalyst, carries out ontology under identical reaction conditions
Polymerization.The 6-caprolactone of respectively 5.7g (50mmol) is respectively placed in 50mL flasks, and 0.2mmol metal complexs are added,
0.1mmol benzyl alcohols.Oil bath heating at 120 DEG C.Isothermal reaction 2 hours, cooling, sampling analysis, conversion ratio is surveyed with liquid chromatogram
, molecular weight is measured (polystyrene is standard specimen) using GPC.The experimental result of embodiment 1-10 is shown in Table 1.
The monomer of 6-caprolactone described in embodiment 1-10 is the higher production of purity after rectifying in caprolactone production process
Product.
Bulk polymerization under the effect of 1 different catalysts of table
Embodiment 11-15
Using the metal complex in above-described embodiment 1 as catalyst in embodiment 11-15, under condition of different temperatures
Carry out bulk polymerization.The 6-caprolactone of 5.7g (50mmol) is respectively placed in 50mL flasks respectively, 0.2mmol embodiments 1 are added
Middle metal complex, 0.1mmol benzyl alcohols.Oil bath heating at a temperature of 5 kinds, isothermal reaction 2 hours is cooling, sampling analysis, conversion
Rate is measured with liquid chromatogram, and molecular weight is measured (polystyrene is standard specimen) using GPC.The experimental result of embodiment 11-15 is shown in Table 2.
The monomer of 6-caprolactone described in embodiment 11-15 is the higher production of purity after rectifying in caprolactone production process
Product.
Polymerization result under 2 different temperatures of table
Embodiment 16-20
Using the metal complex in above-described embodiment 2 as catalyst in embodiment 16-20, in different catalysts dosage
Under the conditions of carry out bulk polymerization.The 6-caprolactone of 5.7g (50mmol) is respectively placed in 50mL flasks respectively, is added in embodiment 2
5 batch quality of metal complex, 0.1mmol benzyl alcohols.The oil bath heating at 120 DEG C.Isothermal reaction 2 hours, cooling, sampling
Analysis, conversion ratio are measured with liquid chromatogram, and molecular weight is measured (polystyrene is standard specimen) using GPC.The experiment knot of embodiment 16-20
Fruit is shown in Table 3.
The monomer of 6-caprolactone described in embodiment 16-20 is the higher production of purity after rectifying in caprolactone production process
Product.
Influence of the 3 metal complex different amounts of table to aggregate rate
Embodiment 21-30
Using the metal complex in above-described embodiment 1 as catalyst in embodiment 21-30, in different organic solvents item
Polymerisation in solution is carried out under part.The 6-caprolactone of 5.7g (50mmol) is respectively placed in 50mL flasks respectively, is added different organic molten
Agent 15mL.Metal complex 0.5mmol, 0.5mmol benzyl alcohol in embodiment 1 is added.Room temperature isothermal reaction 8 hours, sampling point
Analysis, conversion ratio are measured with liquid chromatogram, and final product, which pours into ice methanol, is precipitated white solid, and molecular weight measures (polyphenyl second with GPC
Alkene is standard specimen).The experimental result of embodiment 21-30 is shown in Table 4.
The monomer of 6-caprolactone described in embodiment 21-30 is the higher production of purity after rectifying in caprolactone production process
Product.
Table 4：It polymerize situation in different organic solvents
Embodiment 31-34
Embodiment 31-34 using above-described embodiment 3 metal complex be used as catalyst, be catalyzed 4 kinds of different cyclic esters into
Row bulk polymerization., respectively by 4 kinds, the cyclic ester of 5g is respectively placed in 50mL flasks, and polymerization inhibitor in 1mg embodiments 3 is added, 120 DEG C
Lower oil bath heating is reacted 4 hours, cooling, the content of sampling analysis cyclic ester.Cyclic ester conversion ratio (i.e. aggregate rate) is calculated with this,
The experimental result of embodiment 31-34 is shown in Table 5.
The polymerization of the different cyclic ester monomers of table 5
Claims (9)
1. being catalyzed purposes of the metal complex of cyclic ester polymerization in being catalyzed cyclic ester polymerization, which is characterized in that the metal combination
Object is the compound for having 1 structure of formula：
Wherein, R1、R2、R3、R4It is each independently selected from C1–C30Chain alkyl, C3–C8Cycloalkyl group, C2–C8Alkene
Base, C2–C5Alkynes base,
R5、R6It is each independently selected from C1–C5Alkyl, C1–C5Alkoxy or hydrogen atom；
M is Sn, Mg, Ca or Zn；The metal complex can be in the polymerisation of cyclic ester as the catalyst to using, together
When the catalytic activity that coinitiator carrys out intensified response can be added.
2. being catalyzed the metal complex of cyclic ester polymerization, which is characterized in that the metal complex is the chemical combination for having 2 structure of formula
Object：
Wherein, R7、R8It is each independently selected from C1–C30Chain alkyl, C3–C8Cycloalkyl group, C2–C8Alkylene, C2–
C5Alkynes base,
R5、R6It is each independently selected from C1–C5Alkyl, C1–C5Alkoxy or hydrogen atom；
M is Sn, Mg, Ca or Zn.
3. a kind of purposes of metal complex as claimed in claim 2 in being catalyzed cyclic ester polymerization, which is characterized in that such as right
It is required that metal complex described in 2 can be in the polymerisation of cyclic ester as the catalyst to use, while it can be added and draw altogether
Hair agent carrys out the catalytic activity of intensified response.
4. purposes according to claim 1 or 3, which is characterized in that the coinitiator be MeOH, EtOH,nPrOH、iPrOH、nBuOH、tBuOH、BnOH、Ph2CHOH、Ph3COH、Ph(CH2OH)3、N(CH2CH2OH)3One or more of.
5. purposes according to claim 1 or 3, which is characterized in that metal complex as claimed in claim 1 or 2 can
For stabilizer in the bulk technique of cyclic ester polymerization, can also be added in the process, the stabilizer is trialkyl
Phosphorous acid, the diphosphorous acid that cyclic nonaromatics that alkyl phosphorous acid, aromatic series phosphorous acid, space are obstructed, space are obstructed
The amination that compound, hydroxy phenylpropionic acid, hvdroxvbenzvl compounds, alkylidene bisphenols, alkyl phenol, amino acid, thioether, space are obstructed
Close one or more of object, hydroquinone mixture.
6. purposes according to claim 1 or 3, which is characterized in that metal complex as claimed in claim 1 or 2 can
For deicer in the bulk technique of cyclic ester polymerization, can also be added in the process, the deicer is clay, oxygen
Change one or more of aluminium, silica gel, zeolite, calcium chloride, calcium carbonate, sodium sulphate, calcium bicarbonate, sodium bicarbonate, saleratus
Mixture.
7. purposes according to claim 1 or 3, which is characterized in that metal complex as claimed in claim 1 or 2 can
For in the solution polymerization process of cyclic ester polymerization, polymerisation carries out in organic solvent, the organic solvent is selected from benzene, first
Benzene, dimethylbenzene, N,N-dimethylformamide, chloroform, dichloromethane, acetonitrile, pyridine, dimethyl sulfoxide, 1,4- dioxanes
In one kind, furans, tetrahydrofuran.
8. purposes according to claim 1 or 3, which is characterized in that metal complex as claimed in claim 1 or 2 is suitable
Ring-opening polymerisation for being catalyzed cyclic ester structural compounds.
9. purposes according to claim 1 or 3, which is characterized in that the cyclic ester is selected from the ring-typeization with 3 structure of formula
One or more of monomer adduct：
Wherein, A is-(CH2)5—、—(CH2)4—、—(CH2)3- or-CH2CH(CH3)CH2—；X is O；
Either selected from one or more of the cyclic compound monomer with 4 structure of formula：
Wherein, A, B are [- (CR11R12)—]n, the integer that n is 2~6, A and B can be the same or different；
R11、R12Alkyl selected from H, with 1~5 carbon atom replaces with 1~5 carbon atom and by halogen atom or hydroxyl
Alkyl；X is selected from O or NH.
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