CN107446122A - A kind of functional polycarbonates and preparation method thereof - Google Patents
A kind of functional polycarbonates and preparation method thereof Download PDFInfo
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- CN107446122A CN107446122A CN201710680894.7A CN201710680894A CN107446122A CN 107446122 A CN107446122 A CN 107446122A CN 201710680894 A CN201710680894 A CN 201710680894A CN 107446122 A CN107446122 A CN 107446122A
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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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
- C08G64/0291—Aliphatic polycarbonates unsaturated
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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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/42—Chemical after-treatment
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Abstract
The invention provides a kind of preparation method of functional polycarbonates, including：Carbon dioxide and epoxides are subjected to copolyreaction in the presence of catalyst, obtain makrolon；One or more of the catalyst in schiff bases cobalt complex, rare earth ternary complexes, zinc cobalt dual-metal cyanide complex, salicylic alidehyde imine cobalt or chromic compound, Zinc polycarboxylate composition and diimine Zn complex；The oxycompound includes the epoxides containing double bond；With sulfhydryl compound double bond sulfydryl click-reaction occurs in the presence of initiator for makrolon, obtains the makrolon of functionalization.The present invention uses the epoxides containing double bond to polymerize for raw material with carbon dioxide, the makrolon of biodegradable functionalization by one pot process, so as to avoiding the cumbersome synthesis of six-membered cyclic carbonates and the use of poisonous phosgene derivative；Polymer architecture can accurately be controlled using the polymerization of the present invention simultaneously.
Description
Technical field
The present invention relates to technical field of polymer, more particularly, to a kind of functional polycarbonates and preparation method thereof.
Background technology
In recent decades, as developing rapidly for polymer science flies with the prominent of modern pharmacy, biology and engineering science
Push ahead vigorously, the research of biological medical polymer material is developed rapidly.Wherein biodegradable high polymer material, due to
Second operation taking-up is not required to after implanting, thus in operation suture thread, artificial skin, artificial blood vessel, drug controlled release
And bio-imaging field is widely applied.
Fatty poly-ester carbonate is a kind of important biodegradable/absorption high polymer material, has good biofacies
Capacitive and physical and mechanical properties, and species is various, structure is adjustable, can meet different needs.Importantly, makrolon
Carbon dioxide and neutral alcohol are generated after degraded, the PLA being widely used in biomedical materials field can be avoided
With the adverse reaction in degradation process caused by caused carboxylic-acid substance such as polyglycolic acid.
In recent years, the synthesis on the fatty poly-ester carbonate containing functionalization side base such as amino is reported extensively with application
Road.Such method is typically using the six-membered cyclic carbonates monomer containing substituent as raw material, carries out ring-opening polymerisation, obtains side
Chain contains the makrolon of functional group.But six-membered cyclic carbonates synthesis is complicated disclosed in prior art, even with
The phosgene derivative of severe toxicity, the demand for development of Green Chemistry is not met；In addition, the poly- carbonic acid obtained by ring-opening polymerization method
Ester structure is difficult accurately to control, and cannot get block copolymer.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of functional polycarbonates and its preparation side
Method, the functional polycarbonates prepared by preparation method provided by the invention avoid the cumbersome conjunction of six-membered cyclic carbonates
Into, avoid the use of poisonous phosgene derivative, and can accurately control the structure of polymer.
The invention provides a kind of functional polycarbonates, are structure shown in formula (I)：
Wherein, A is structure shown in formula (a)~formula (d)：
Wherein, m=0.05~1, n=0~0.95, m+n=1；
R1Selected from H, methyl, ethyl or phenyl；R5For H or methyl；
Q is the structure that sulfhydryl compound is formed with dehydrogenation after double bond reaction.
Preferably, m=0.3~0.7, n=0.3~0.7, m+n=1；
The sulfhydryl compound is the compound containing a sulfydryl and one or more hydroxyls, a sulfydryl and one
Or compound, the compound of a sulfydryl and one or more amino, a sulfydryl and the one or more amino of multiple carboxyls
The compound of acid or the fluorescence molecule containing sulfydryl.
The invention provides a kind of preparation method of functional polycarbonates, including：
Carbon dioxide and epoxides are subjected to copolyreaction in the presence of catalyst, obtain makrolon；It is described to urge
Agent is selected from schiff bases cobalt complex, rare earth ternary complexes, zinc-cobalt dual-metal cyanide complex, salicylic alidehyde imine cobalt or chromium
One or more in complex, Zinc polycarboxylate composition and diimine Zn complex；The oxycompound includes containing double bond
Epoxides；
With sulfhydryl compound double bond-sulfydryl click-reaction occurs in the presence of initiator for the makrolon, obtains function
The makrolon of change.
Preferably, the epoxides also includes the epoxides for not containing double bond.
Preferably, the epoxides containing double bond is selected from pi-allyl -2,3- glycidyl ethers, 4- vinyl epoxy rings
One or more in hexane, 3,4- epoxy radicals -1- butylene and limonene oxide；The not double bond containing epoxides is selected from
One or more in oxirane, expoxy propane, epoxy butane, styrene oxide, cyclohexene oxide and cyclopentene oxide.
Preferably, the pressure of the copolyreaction is 0.1~5.0Mpa；The temperature of the copolyreaction is 10 DEG C~150
℃。
Preferably, in the catalyst in the molal quantity and epoxides of metallic element the molal quantity of epoxy monomer ratio
For (20~40)：(500~1000).
Preferably, the sulfhydryl compound is the compound containing a sulfydryl and one or more hydroxyls, a sulfydryl
The compound of compound, a sulfydryl and one or more amino with one or more carboxyls, a sulfydryl and one or more
The compound of individual amino acid or the fluorescence molecule containing sulfydryl.
Preferably, the double bond-sulfydryl click-reaction is 0.1~5h of 0.1~60h of thermal initiation or ultraviolet light.
Preferably, the initiator is radical initiator.
Compared with prior art, the invention provides a kind of preparation method of functional polycarbonates, including：By dioxy
Change carbon and epoxides carries out copolyreaction in the presence of catalyst, obtain makrolon；The catalyst is selected from schiff bases
Cobalt complex, rare earth ternary complexes, zinc-cobalt dual-metal cyanide complex, salicylic alidehyde imine cobalt or chromic compound, zinc polycarboxylate
One or more in complex and diimine Zn complex；The oxycompound includes the epoxides containing double bond；Poly- carbon
With sulfhydryl compound double bond-sulfydryl click-reaction occurs in the presence of initiator for acid esters, obtains the makrolon of functionalization.This
Invention uses the epoxides containing double bond to polymerize for raw material with carbon dioxide, is biodegradable by one pot process
The makrolon of functionalization, so as to avoid the cumbersome synthesis of six-membered cyclic carbonates and the use of poisonous phosgene derivative；
Polymer architecture can accurately be controlled using the polymerization of the present invention simultaneously；Double bond-sulfydryl click-reaction of the present invention simultaneously
Metal residual can be removed well, there is huge application prospect in field of biomedical polymer materials.
Brief description of the drawings
Fig. 1 is nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure of functional polycarbonates prepared by the embodiment of the present invention 2；
Fig. 2 is nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure of functional polycarbonates prepared by the embodiment of the present invention 3；
Fig. 3 is nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure of functional polycarbonates prepared by the embodiment of the present invention 4；
Fig. 4 is nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure of functional polycarbonates prepared by the embodiment of the present invention 5；
Fig. 5 is nucleus magnetic hydrogen spectrum (1HNMR, DMSO) figure of functional polycarbonates prepared by the embodiment of the present invention 6；
Fig. 6 is nucleus magnetic hydrogen spectrum (1HNMR, DMSO) figure of functional polycarbonates prepared by the embodiment of the present invention 7；
Fig. 7 is nucleus magnetic hydrogen spectrum (1HNMR, DMSO) figure of functional polycarbonates prepared by the embodiment of the present invention 8；
Fig. 8 is the efficient liquid phase spectrogram of functional polycarbonates-adriamycin prepared by the embodiment of the present invention 9.
Embodiment
The invention provides a kind of functional polycarbonates, are structure shown in formula (I)：
Wherein, A is structure shown in formula (a)~formula (d)：
Wherein, m=0.05~1, n=0~0.95, m+n=1；Preferably, m=0.3~0.7, n=0.3~0.7, m+n
=1.M, n is mol ratio.
R1Selected from H, methyl, ethyl or phenyl；R5For H or methyl；
Q is the structure that sulfhydryl compound is formed with dehydrogenation after double bond reaction.
According to the present invention, the functional polycarbonates preferably have following structure：
Wherein, m=0.05~1, n=0~0.95, m+n=1；X=0.05~1, y=0~0.95, x+y=1；It is preferred that
, m=0.3~0.7, n=0.3~0.7, m+n=1；X=0.3~0.7, y=0.3~0.7, x+y=1.
R2It is preferably selected from H, methyl, ethyl or phenyl；R4It is preferably selected from H, methyl, ethyl or phenyl； R5Preferably H or first
Base
The sulfhydryl compound is the compound containing a sulfydryl and one or more hydroxyls, a sulfydryl and one
Or the compound of multiple carboxyls, the compound of a sulfydryl and one or more amino, a sulfydryl and one or more amino
The compound of acid or the fluorescence molecule containing sulfydryl.
The present invention, without limiting, meets above-mentioned condition, included but is not limited to for the sulfhydryl compound：Mercapto
Guanidine-acetic acid, 3- mercaptopropionic acids, mercaptobenzoic acid or 2- dimercaptosuccinic acids, mercaptoethylmaine, 3- sulfydryl -1- propylamine, 2- mercaptoacetyls
Amine, 4,5- dimethoxy -2- sulfydryl benzene methanamine hydrochlorides.
According to the present invention, the functional polycarbonates backbone polymerization degree is preferably 10~300；Molecular weight distribution is
1.02~3；More preferably 1.01~1.3；Makrolon is prepared especially with different catalyst and different epoxides
When, molecular weight distribution is different.
The invention provides a kind of preparation method of functional polycarbonates, including：
Carbon dioxide and epoxides are subjected to copolyreaction in the presence of catalyst, obtain makrolon；It is described to urge
Agent is selected from schiff bases cobalt complex, rare earth ternary complexes, zinc-cobalt dual-metal cyanide complex, salicylic alidehyde imine cobalt or chromium
One or more in complex, Zinc polycarboxylate composition and diimine Zn complex；The oxycompound includes containing double bond
Epoxides；
With sulfhydryl compound double bond-sulfydryl click-reaction occurs in the presence of initiator for the makrolon, obtains function
The makrolon of change.
The preparation method of functional polycarbonates provided by the invention is first by carbon dioxide and epoxides in catalyst
In the presence of carry out copolyreaction, obtain makrolon；
According to the present invention, the epoxides also includes the epoxides for not containing double bond.That is, the present invention is
Carbon dioxide, the double bond containing epoxides binary copolymerization of bag；Or carbon dioxide, the double bond containing epoxides of bag and be free of
The random copolymerization of epoxides ternary or block copolymerization of double bond.So as to obtain the polymer containing side base double bond.So as to obtain：
Backbone polymerization degree is preferably 10~300；Molecular weight distribution is 1.02~3；More preferably 1.01~1.3；Especially with difference
Catalyst and different epoxides when prepare makrolon, molecular weight distribution is different.
According to the present invention, the epoxides containing double bond is preferably selected from pi-allyl -2,3- glycidyl ethers, 4- ethene
One or more in base 7-oxa-bicyclo[4.1.0,3,4- epoxy radicals -1- butylene and limonene oxide；The not double bond containing epoxy
Compound is preferably selected from oxirane, expoxy propane, epoxy butane, styrene oxide, cyclohexene oxide and cyclopentene oxide
It is one or more.
Catalyst of the present invention is selected from schiff bases cobalt complex, rare earth ternary complexes, zinc-cobalt dual-metal cyaniding network
One or more in compound, salicylic alidehyde imine cobalt or chromic compound, Zinc polycarboxylate composition and diimine Zn complex.
The present invention, without limiting, can be commercially available, can also use for the source of above-mentioned catalyst and epoxides
It is prepared by method well known to those skilled in the art.
According to the present invention, carbon dioxide and epoxides carry out copolyreaction preferably anhydrous in the presence of catalyst
Carried out under oxygen free condition, water content is below 100ppm.Reaction of the present invention is preferably carried out in a kettle.
Wherein, can obtain using schiff bases cobalt complex, diimine Zn complex and salicylic alidehyde imine cobalt or chromic compound
HMW (degree of polymerization is about 30~300), narrow ditribution (PDI ＜ 1.5) full alternating structure makrolon.
It can be catalyzed to obtain high score using zinc-cobalt dual-metal cyanide complex, zinc polycarboxylate and diethyl zinc-more Proton Systems
Son amount (degree of polymerization is about 50~300), the makrolon of wide distribution (MWD ＜ 4).
It is above-mentioned so that carbonate polymer structure-controllable of the present invention.
According to the present invention, catalyst amount is preferably：Epoxy in the molal quantity and epoxides of metallic element in catalyst
The ratio of the molal quantity of monomer is preferably (20~40)：(500~1000)；More preferably (30~40)：(500~700).
The CO2 partial pressures of copolyreaction are preferably 0.1~5.0MPa, more preferably 1~3Mpa；The reaction temperature is preferred
For 10~150 DEG C, more preferably 20~80 DEG C, the reaction time is preferably 1~100 hour, more preferably 1~50 hour；
Most preferably 10~40 hours.
The copolyreaction can be carried out under body or solution reaction, and when using solution copolymerization, the solvent is preferred
For toluene, tetrahydrofuran, dioxane and chlorine alkane substitute class solvent.
It is preferably after reaction：Using crude product after dichloromethane dissolving copolyreaction, polymer is settled out in methyl alcohol,
Repeated precipitation is multiple.
According to the present invention, a portion embodiment：
When binary copolymerization, by CO2, double bond containing epoxides one kettle way combined polymerization.Catalyst is preferably salicylide Asia
Amine cobalt complex, catalyst amount are that the mol ratio of metal and epoxy monomer is (20~40) in catalyst：(500~1000)；
More preferably (30~40)：(500~700)；Most preferably 100: 500.Post-processing is reacted typically to dissolve using dichloromethane
Crude product, is settled out polymer in methyl alcohol, and repeated precipitation is multiple.
According to the present invention, a portion embodiment：
When ternary random copolymerization, by CO2, double bond containing epoxides and not double bond containing epoxides one kettle way be total to
Polymerization.
Wherein, the mol ratio of double bond containing epoxides and not double bond containing epoxides can be adjusted according to practical application,
Preferably 1:50~50:1.Catalyst is preferably salicylic alidehyde imine cobalt complex, and catalyst amount is metal and ring in catalyst
The mol ratio of oxygen monomer is (20~40)：(500~1000)；More preferably (30~40)：(500~700)；Most preferably 100
∶500.Post-processing is reacted typically using dichloromethane dissolving crude product, is settled out polymer in methyl alcohol, repeated precipitation is more
It is secondary.
According to the present invention, a portion embodiment：
When tri-block is copolymerized, first by CO2Not double bond containing epoxides carries out binary copolymerization.To ensure gained
Polymer architecture is controllable, and a certain amount of initiator containing active hydrogen is typically added in polymerization system, and the initiator is preferably water, two
First alcohol and dicarboxylic acids；The initiator dosage is preferably：The mol ratio of initiator and metal in catalyst is 50：1, it is more excellent
Elect 20 as：1.
To ensure that epoxides converts completely, polymerisation in solution is typically carried out.The solvent is preferably toluene and dichloromethane
Mixed solution, volume ratio is preferably 1：1；The volume ratio of the mixed solvent and epoxy monomer is preferably 1：1；The solution
Polymerization time is preferably 48~72 hours.After polymerization terminates, (operated under the conditions of anhydrous and oxygen-free in glove box), to condensate
A certain proportion of epoxides containing double bond, double bond containing epoxides and not double bond containing epoxides are added in system
Mol ratio can be adjusted according to practical application, and preferably 1:50~50:1.It is typically thick using dichloromethane dissolving to react post-processing
Product, polymer is settled out in methyl alcohol, repeated precipitation is multiple, drying.
After obtaining makrolon, with sulfhydryl compound double bond-sulfydryl point occurs in the presence of initiator for the makrolon
Reaction is hit, obtains the makrolon of functionalization.
According to the present invention, the double bond-sulfydryl click-reaction is preferably specially：Makrolon is with sulfhydryl compound certainly
By being reacted in the presence of base initiator, the makrolon of functionalization is obtained.
The makrolon of the functionalization be preferably containing pendant hydroxyl group, amino, amino acid, carboxyl makrolon.
The double bond-sulfydryl click-reaction is preferably 0.1~5h of 0.1~60h of thermal initiation or ultraviolet light.More preferably
For 1~5h of 1~50h of thermal initiation or ultraviolet light.The radical initiator includes but is not limited to BPO, AIBN or DMPA certainly
By base initiator.The present invention for its source without limit, it is preferably commercially available.
It is preferably to filter, rotate to obtain functional polycarbonates after reaction.
According to the present invention, the sulfhydryl compound is preferably the compound containing a sulfydryl and one or more hydroxyls,
The compound of the compound of one sulfydryl and one or more carboxyls, a sulfydryl and one or more amino, sulfydryl and
The compound of one or more amino acid or the fluorescence molecule containing sulfydryl.
Wherein, the compound containing a sulfydryl and one or more hydroxyls be preferably mercaptoethanol, 3- sulfydryls-
1,2-PD, mercapto-polyglycol or sulfydryl monose；The compound of one sulfydryl and one or more carboxyls is preferably
TGA, 3- mercaptopropionic acids, mercaptobenzoic acid or 2- dimercaptosuccinic acids；One sulfydryl and one or more amino
Compound mercaptoethylmaine, 3- sulfydryl -1- propylamine, 2- mercaptoacetylamides, 4,5- dimethoxy -2- sulfydryl benzene methanamine hydrochlorides.
The makrolon of the double bond containing side base with above-mentioned sulfhydryl compound in the presence of a free-radical initiator, it is anti-through thermal initiation
Should or ultraviolet irradiation initiation reaction, can obtain the makrolon of side base functionalization.
Wherein, the reaction is carried out preferably in oxygen-free environment；The reaction dissolvent be preferably tetrahydrofuran, toluene or
Dioxane.
When thermal initiation, BPO and AIBN etc. commercially available radical initiator can be used, and now, the temperature is preferably
60~80 DEG C, the reaction time is preferably 10~20 hours.
When ultraviolet irradiation initiation reaction, the commercially available radical initiator such as DMPA is used；The uviol lamp power is preferred
For 10~200 watts, exposure time is preferably 2~3 hours.
In the present invention, the mol ratio of the addition of contained double bond and sulfhydryl compound is preferably 1 in the makrolon：
40；The addition of the initiator is preferably 30% of double bond molal quantity in makrolon；The present invention is even in order to avoid free radical
Conjunction causes macromolecules cross-linking, and macromolecular concentration is controlled in below 5wt%, while needs to add excessive sulfhydryl compound, is preferably
It is excessive 20 times.Unreacted sulfhydryl compound can pass through the means recyclings such as distillation.
By above-mentioned double bond-sulfydryl click-reaction, the metal remained in polymer can remove the present invention substantially, so as to
Be advantageous to bio-medical.
After above-mentioned side base functional polycarbonates are obtained, polymer can be self-assembled into nano particle in aqueous, enter
Row bio-medical；Also modified after can continuing again on the basis of this, connect fluorescence molecule, polymer, medicine, bioactive peptide or other
Molecule reaction with bioactivity, for biological field, solving practical problems.With preparing work(using six-membered cyclic carbonates
Energy property makrolon is compared, and the present invention has significantly beneficial technique effect：
The present invention uses commercialized double bond containing epoxides as raw material, with CO2Polymerization, one kettle way obtains can biology
The makrolon of degraded, so as to avoid the cumbersome synthesis of six-membered cyclic carbonates and the use of poisonous phosgene derivative；This hair
The polymerization of bright use, by one kettle way sequential feeds, polymer architecture can be accurately controlled, this gathers for traditional open loop
It is difficult to realize for conjunction；The double bond that the present invention uses-sulfydryl click-reaction can be very good to remove metal residual, so as to favourable
In bio-medical.
The synthetic method of the present invention effectively solves conventional circular carbonic acid Lipase absobed complexity, resulting polymers structure not
The problems such as controllable, can be easy, controllable obtain the makrolon of metal-free complete biodegradable, and modified after being easy to, in life
There is huge application prospect in thing medical macromolecular materials field.
The invention provides a kind of preparation method of functional polycarbonates, including：Carbon dioxide and epoxides are existed
Copolyreaction is carried out in the presence of catalyst, obtains makrolon；The catalyst is selected from schiff bases cobalt complex, rare earth three
First complex, zinc-cobalt dual-metal cyanide complex, salicylic alidehyde imine cobalt or chromic compound, Zinc polycarboxylate composition and diimine zinc
One or more in complex；The oxycompound includes the epoxides containing double bond；Makrolon and sulfhydryl compound
Double bond-sulfydryl click-reaction occurs in the presence of initiator, obtains the makrolon of functionalization.The present invention, which uses, contains double bond
Epoxides polymerize with carbon dioxide for raw material, the makrolon of biodegradable functionalization by one pot process,
So as to avoid the cumbersome synthesis of six-membered cyclic carbonates and the use of poisonous phosgene derivative；Simultaneously using the poly- of the present invention
Conjunction method can accurately control polymer architecture.
In order to further illustrate the present invention, with reference to embodiments to functional polycarbonates material provided by the invention
It is described in detail.
The synthesis of embodiment 1Salen Co (III)-TFA catalyst
The synthesis of Salen Co (III)-TFA catalyst includes step：
The preparation of N, N '-two (3,5- di-tert-butyl salicylaldehydes) contracting -1,2- cyclohexanediamine：To equipped with magnetic agitation, backflow
Sequentially added in the 500mL three-necked flasks of condenser pipe and constant pressure funnel 3,5- di-tert-butyl salicylaldehydes (34.85g,
0.1mol) with 200mL ethanol, 60 DEG C or so are heated to, stirring is allowed to be completely dissolved.By anti-form-1,2- cyclohexanediamine (5.7g,
40mL ethanol 0.05mol) is dissolved in, is slowly dropped in the ethanol solution of salicylide, after being added dropwise, is heated to reflux 6h, is cooled down
To room temperature, stand overnight.Mixture is filtrated to get yellow solid, is then dried in vacuo at 40 DEG C, yield 95%.
Salen Co (II) preparation：Under Ar gas shieldeds, to the 250mL equipped with constant pressure funnel and magnetic agitation
Add N in three-necked flask, (3,5- di-tert-butyl salicylaldehydes) contracting -1,2- cyclohexanediamine of N '-two (3.65 g, 6.67mmol) and
Dichloromethane refined 25mL, stirring are allowed to dissolve.By anhydrous Co (AcO)2Ethanol solution (1.42g, 8.0mmol, 30mL)
It is slowly dropped to by constant pressure funnel in half an hour in flask.With Co (AcO)2Add, there are a large amount of red solids to analyse
Go out.It is added dropwise, the dichloromethane refined with 5 mL rinses constant pressure funnel, continues to stir 15min.It is allowed to using ice-water bath
Temperature of reaction system is down to 0 DEG C, keeps 30min.The press filtration under Ar gas shieldeds, precipitation is washed for several times with methanol, then 40
It is dried in vacuo at DEG C, yield 80%.
The preparation of Salen Co (III)-TFA catalyst：Under Ar gas shieldeds, to the 50 mL single port bottles wrapped up with masking foil
The dichloromethane that middle addition Salen Co (II) (90mg, 0.15mmol) and 15mL are refined, stirring are allowed to dissolve.Add trifluoro
Silver acetate (33mg, 0.15mmol), after stirring 24 hours at room temperature, silver-colored impurity is filtered out, solution is spin-dried for and obtains product, Ran Hou
Standby, yield 93% is dried in vacuo at 40 DEG C.
The preparation of Salen Co (III)-Cl catalyst：Under Ar gas shieldeds, to the 50 mL single port bottles wrapped up with masking foil
The dichloromethane that middle addition Salen Co (II) (90mg, 0.15mmol) and 15mL are refined, stirring are allowed to dissolve.Add dense salt
Sour (1ml, 11.6mmol), after stirring 24 hours at room temperature, be spin-dried for solution and obtain product, be then dried in vacuo at 40 DEG C it is standby,
Yield 90%.
The synthesis of double (triphenyl phosphorus) trifluoroacetates：Under Ar gas shieldeds, to the 50mL single port bottles wrapped up with masking foil
Middle to add the refined dichloromethane of double (triphenyl phosphorus) chlorates (86mg, 0.15mmol) and 15mL, stirring is allowed to dissolve.Add
Enter Silver Trifluoroacetate (33mg, 0.15mmol), after stirring 24 hours at room temperature, filter out silver-colored impurity, be spin-dried for solution and obtain product,
Then it is dried in vacuo at 40 DEG C standby, yield 97%, is designated as PPNTFA.
The preparation of the double bond containing bipolymer of the side base of embodiment 2
In CO2 atmosphere, by Salen Co (III)-TFA (100mg, 0.138mmol), PPNTFA (92 mg,
0.138mmol) added with 4 vinyl epoxy cyclohexane (VCHO) 20ml (150mmol) in the reactor dried to 100ml
(monomer water content 80ppm), reaction pressure 2.5MPa, temperature are 25 DEG C, and after mechanic whirl-nett reaction 20h, slowly release is pressed
Power, take out crude product.Decompression separates unreacted VCHO, uses CH again2Cl2Crude product is dissolved, is precipitated in methanol, so repeatedly 3-
It is put into vacuum drying oven and is dried to constant weight after 5 times.Weight method calculate VCHO conversion ratio be 60%, by Salen Co (III)-
When TFA replaces with equimolar SalenCo-Cl catalyst, yield is only 48%.GPC test obtain the makrolon relative number it is equal
Molecular weight is 26600, and molecular weight distribution is 1.25 (THF is mobile phase).Its1HNMR spectrograms are shown in Fig. 1.Fig. 1 is implemented for the present invention
Nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure of functional polycarbonates prepared by example 2.
The preparation of the double bond containing ternary atactic copolymer of the side base of embodiment 3
In CO2 atmosphere, by Salen Co (III)-TFA (50mg, 0.07mmol), PPNTFA (46mg,
0.07mmol), 4 vinyl epoxy cyclohexane (VCHO) (4ml, 30mmol) and expoxy propane (PO) (4.9ml, 70mmol) add
Enter in the reactor dried to 20ml (monomer water content 80ppm), reaction pressure 2.5MPa, temperature is 25 DEG C, mechanical agitation
After reacting 15h, pressure is slowly discharged, takes out crude product.Decompression separates unreacted VCHO, uses CH again2Cl2Dissolve crude product,
Precipitated in methanol, be put into vacuum drying oven and dried to constant weight after so repeating 3-5 times.Weight method calculates ternary atactic copolymer
Conversion ratio be 77%, when Salen Co (III)-TFA is replaced with into equimolar SalenCo-Cl catalyst, yield 52%.
GPC test obtain the makrolon relative number-average molecular weight be 54000, molecular weight distribution is 1.20 (THF is mobile phase).Its1HNMR spectrograms are shown in Fig. 2.Fig. 2 is the nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) of functional polycarbonates prepared by the embodiment of the present invention 3
Figure.
The preparation of the double bond containing ternary block polymer of the side base of embodiment 4
In CO2 atmosphere, by Salen Co (III)-TFA (8.9mg, 0.0125mmol), PPNTFA (8.2 mg,
0.0125mmol), expoxy propane (PO) (0.87ml, 12.5mmol), initiator decanedioic acid (50mg, 0.25mmol), 0.3ml
Toluene and 0.3ml CH2CL2Add in the reactor dried to 10ml (monomer water content 80ppm), reaction pressure 2.5MPa,
Temperature is 25 DEG C, after mechanic whirl-nett reaction 48h (reaction completely), slowly discharges pressure.Allyl glycidyl is added in N2 atmosphere
Glycerin ether (1.4ml, 12.5mmol), under 2.5MPa, react 48 hours.Use CH2Cl2Crude product is dissolved, is precipitated in methanol, this
Sample is put into vacuum drying oven after repeating 3-5 times and dried to constant weight.Weight method calculate ternary atactic copolymer conversion ratio be>
99%, when Salen Co (III)-TFA is replaced with into equimolar SalenCo-Cl catalyst, yield 85%.GPC is tested
The relative number-average molecular weight of the makrolon is 12000, and molecular weight distribution is 1.04 (THF is mobile phase).Its1HNMR spectrograms
See Fig. 3.Fig. 3 is nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure of functional polycarbonates prepared by the embodiment of the present invention 4.
The preparation of the double bond containing ternary block polymer of the side base of embodiment 5
It is to change allyl glycidyl ether into 4- vinyl epoxy rings using with the identical method of embodiment 4, difference
Hexane (0.32ml, 2.5mmol) and expoxy propane (0.67ml, 10mmol).GPC test obtain the makrolon relative number it is equal
Molecular weight is 12000, and molecular weight distribution is 1.04 (THF is mobile phase).Its1HNMR spectrograms are shown in Fig. 4.Fig. 4 is implemented for the present invention
Nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure of functional polycarbonates prepared by example 5.
6 double bonds of embodiment-sulfydryl click-reaction
Makrolon (equivalent to 8.93mmol C=C) in 1.5g embodiments 2 and 40mlTHF are added into tri- mouthfuls of 150ml
In round-bottomed flask, after stirring makes makrolon dissolving completely, 26g (0.18mol) Boc protections are added under the atmosphere of nitrogen
2-MEA and 0.484g (2.94mmol) AIBN, it is rapidly heated to 70 DEG C after it is well mixed, reacts at such a temperature
Stop reaction after 24h, gained crude product is filtered, after revolving, is settled out polymer in methyl alcohol, and precipitation uses THF- methanol again
It is put into vacuum drying oven and is dried to constant weight after handling 3-5 times.GPC tests the relative number-average molecular weight for obtaining the macromole evocating agent
For 46000, molecular weight distribution is 1.20 (THF is mobile phase).
2-MEA Boc is protected：2-MEA (19.25g, 250mmol) is dissolved in 150ml water, Xiang Qijia
Enter di-tert-butyl dicarbonate (54.5g, 250mol) THF solution, be stirred at room temperature 4 hours under Ar protections.Aqueous solution CH2Cl2
Extraction, gained organic phase anhydrous Na2SO4Dry, be dried in vacuo to obtain colourless oil liquid (98%).
Polymer takes off Boc reactions：Above-mentioned resulting polymers (0.5g) are dissolved in 2mlTHF, add 30ml thereto
HCl saturation THF solutions, stir 4 hours at room temperature, have white precipitate appearance, gained solid is dissolved in deionized water, freeze
Dry product.Its1HNMR spectrograms are shown in Fig. 5.Fig. 5 is the nucleus magnetic hydrogen spectrum of functional polycarbonates prepared by the embodiment of the present invention 6
(1HNMR, DMSO) figure.
7 double bonds of embodiment-sulfydryl click-reaction
Using the method for embodiment 6, different makrolon and 2- TGAs in using embodiment 3 carries out double
Key-sulfydryl click-reaction.It is worth noting that 2- TGAs do not need Boc protections, it can directly participate in double bond-sulfydryl and click on
Reaction.Its1HNMR spectrograms are shown in Fig. 6.Fig. 6 is the nucleus magnetic hydrogen spectrum of functional polycarbonates prepared by the embodiment of the present invention 7
(1HNMR, DMSO) figure.
8 double bonds of embodiment-sulfydryl click-reaction
Using the method for embodiment 6, the cysteine of different makrolon and Boc protections in using embodiment
Carry out double bond-sulfydryl click-reaction.Resulting polymers take off Boc in HCl saturations THF, obtain colourless polymer.Its1HNMR spectrograms
See Fig. 7.Fig. 7 is nucleus magnetic hydrogen spectrum (1HNMR, DMSO) figure of functional polycarbonates prepared by the embodiment of the present invention 8.
Modified medicaments adriamycin (DOX) after the polymer of embodiment 9
Polymer in embodiment 6 (62.4mg, 0.20mmol-NH2) is dissolved in deionized water (pH=6.5), added
The 2- iminothiolanes hydrochloride (relative to amino) of 0.1 equivalent, stir 2 hours at room temperature.Mixture ultrafiltration removes
Unreacted 2- iminothiolanes hydrochloride.The adriamycin (Mal-DOX) of maleic anhydride modification is added into clear liquid
(9.6mg), pH is adjusted to 6.7, stirs 3 hours at room temperature, then carry out ultrafiltration, obtain makrolon and adriamycin DOX knot
Compound (PPC-DOX).
Mal-DOX preparation：24mg DOX (0.04mmol) and 28mg (N- (ε-maleimidocaproic acid)
Hydrazide, trifluoroacetic acid salt) (EMCH) (0.12 mmol) is dissolved in 12ml and dried in methanol, then adds
Enter 40 microlitres of trifluoroacetic acid, be stirred overnight under lucifuge.Resulting solution is concentrated into 1ml, is deposited in dry ethyl acetate, from
The heart is collected, and vacuum drying is standby.Products therefrom is characterized (see Fig. 8) with high performance liquid chromatography.Fig. 8 is prepared by the embodiment of the present invention 9
Functional polycarbonates-adriamycin efficient liquid phase spectrogram.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of functional polycarbonates, it is characterised in that be structure shown in formula (I)：
Wherein, A is structure shown in formula (a)~formula (d)：
Wherein, m=0.05~1, n=0~0.95, m+n=1；
R1Selected from H, methyl, ethyl or phenyl；R5For H or methyl；
Q is the structure that sulfhydryl compound is formed with dehydrogenation after double bond reaction.
2. makrolon according to claim 1, it is characterised in that the m=0.3~0.7, n=0.3~0.7, m+n
=1；
The sulfhydryl compound is the compound containing a sulfydryl and one or more hydroxyls, a sulfydryl and one or more
The change of the compound of carboxyl, the compound of a sulfydryl and one or more amino, a sulfydryl and one or more amino acid
Compound or the fluorescence molecule containing sulfydryl.
A kind of 3. preparation method of functional polycarbonates, it is characterised in that including：
Carbon dioxide and epoxides are subjected to copolyreaction in the presence of catalyst, obtain makrolon；The catalyst
Coordinate selected from schiff bases cobalt complex, rare earth ternary complexes, zinc-cobalt dual-metal cyanide complex, salicylic alidehyde imine cobalt or chromium
One or more in thing, Zinc polycarboxylate composition and diimine Zn complex；The oxycompound includes the epoxy containing double bond
Compound；
With sulfhydryl compound double bond-sulfydryl click-reaction occurs in the presence of initiator for the makrolon, obtains functionalization
Makrolon.
4. preparation method according to claim 3, it is characterised in that the epoxides also includes the ring for not containing double bond
Oxide.
5. preparation method according to claim 4, it is characterised in that the epoxides containing double bond is selected from allyl
Base -2,3- glycidyl ethers, 4 vinyl epoxy cyclohexane, 3,4- epoxy radicals -1- butylene and one kind or more in limonene oxide
Kind；The not double bond containing epoxides is selected from oxirane, expoxy propane, epoxy butane, styrene oxide, cyclohexene oxide
With the one or more in cyclopentene oxide.
6. preparation method according to claim 3, it is characterised in that the pressure of the copolyreaction is 0.1~5.0Mpa；
The temperature of the copolyreaction is 10 DEG C~150 DEG C.
7. preparation method according to claim 3, it is characterised in that the molal quantity and ring of metallic element in the catalyst
The ratio of the molal quantity of epoxy monomer is (20~40) in oxide：(500~1000).
8. preparation method according to claim 3, it is characterised in that the sulfhydryl compound is to contain a sulfydryl and one
The compound of individual or multiple hydroxyls, the compound of a sulfydryl and one or more carboxyls, a sulfydryl and one or more ammonia
The compound of base, the compound of a sulfydryl and one or more amino acid or the fluorescence molecule containing sulfydryl.
9. preparation method according to claim 3, it is characterised in that the double bond-sulfydryl click-reaction is thermal initiation 0.1
0.1~5h of~60h or ultraviolet light.
10. preparation method according to claim 9, it is characterised in that the initiator is radical initiator.
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| IT202100012149A1 (en) * | 2021-05-12 | 2022-11-12 | Eni Spa | PROCESS FOR THE PREPARATION OF TERPOLYMERS FUNCTIONALIZED BY EPOXIES AND CARBON DIOXIDE. |
| CN115725064A (en) * | 2021-08-30 | 2023-03-03 | 四川大学 | Preparation method of polycarbonate with main chain containing parallel-ring structure |
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