CN110218303A - A kind of method of non-metal catalyst catalysis epoxidation object and cyclic acid anhydride copolymerization aliphatic polyester - Google Patents
A kind of method of non-metal catalyst catalysis epoxidation object and cyclic acid anhydride copolymerization aliphatic polyester Download PDFInfo
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- CN110218303A CN110218303A CN201910563032.5A CN201910563032A CN110218303A CN 110218303 A CN110218303 A CN 110218303A CN 201910563032 A CN201910563032 A CN 201910563032A CN 110218303 A CN110218303 A CN 110218303A
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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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
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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
- C08G63/87—Non-metals or inter-compounds thereof
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Abstract
The invention discloses a kind of methods of non-metal catalyst catalysis epoxidation object and cyclic acid anhydride copolymerization aliphatic polyester, non-metal catalyst and cyclic acid anhydride are placed in a reaction flask, it vacuumizes, epoxides and solvent is sequentially added in the reaction flask, at a certain temperature heating reaction, it is cooled to room temperature, polymer is dissolved out from reaction flask with chloroform, using n-hexane as sedimentation agent, after the product that settles out, it is dried in vacuo under certain temperature, aliphatic polyester is made.The synthetic method synthetic method is using epoxides and cyclic acid anhydride as monomer, post-treated to obtain aliphatic polyester by non-metal catalyst initiated polymerization under conditions of drying, anaerobic；Have many advantages, such as no metal residual, high catalytic efficiency, the good, high yield of selectivity and narrow molecular weight distribution；It is of very high actual application value.
Description
Technical field
The invention belongs to synthesis of polymer material technical field, it is related to a kind of non-metal catalyst catalysis epoxidation object and ring
The method of shape anhydride copolymers synthctic fat adoption ester.
Background technique
With the increasingly development of social economy, plastic products have become article indispensable in daily life.However, general
Logical plastics itself are difficult to degrade, and the processing method of existing scrapped plastic products causes water source, soil, air etc. very big
Pollution, and cause white pollution.Thus, sight is gradually gathered on polyester-based polymer Biodegradable material by people, and
And starch degradation material is overcome the shortcomings of with such material substituted starch class packing material.Polyester-based polymer material packet
Aliphatic degradable polyester and aromatic polyester are included, benzene ring structure of the aromatic polyester due to itself system with rigidity influences
Its degradation property, so that aliphatic polyester becomes research hotspot.Epoxides and cyclic acid anhydride combined polymerization are to generate aliphatic poly
One of effective ways of ester, the aliphatic polyester of synthesis usually have higher molecular weight and relatively narrow molecular weight distribution, have
Biological degradability, good biocompatibility and physical mechanical property, it is nontoxic and pollution-free, and also there are many type.It can also pass through
Change backbone chemistry structure and introduce functional group and further improve its performance, meets the needs of various aspects, meet current environmental protection
Trend.Therefore, which needs to select the suitable catalyst with higher catalytic activity.
Summary of the invention
The object of the present invention is to provide a kind of non-metal catalyst catalysis epoxidation objects and cyclic acid anhydride copolymerization fat
The method of adoption ester.
To achieve the above object, the technical scheme adopted by the invention is that: a kind of non-metal catalyst catalysis epoxidation object
With the method for cyclic acid anhydride copolymerization aliphatic polyester, specifically:
1 ︰ 200~600 in mass ratio takes non-metal catalyst and cyclic acid anhydride respectively, then by dissolution 1g in 300mL solvent without gold
The ratio of metal catalyst takes solvent, then takes volume epoxides identical with solvent volume；By non-metal catalyst and ring-type acid
Acid anhydride is placed in a reaction flask, and is vacuumized, and epoxides and solvent are sequentially added in the reaction flask, and it is 80 that reaction flask, which is placed in temperature,
8~20h is heated in~130 DEG C of environment, is cooled to room temperature, polymer is dissolved out from reaction flask with chloroform, with n-hexane
It for sedimentation agent, after the product that settles out, is dried in vacuo at a temperature of 80~100 DEG C, aliphatic polyester is made.
Non-metal catalyst uses small molecule Porphyrin and its derivative, comprising: tetraphenylporphyrin (TPP) No. CAS: 917-
23-7；5,10,15,20- tetra- (4- bromophenyl) porphyrins (TBPP), No. CAS: 29162-73-0；meso- four [4(or 5)-imidazoles
Base] porphyrin (TImp) porphyrin small molecule compound.The structural formula of non-metal catalyst formula 1 described as follows, formula 2, formula 3 or formula
Shown in 4:
Formula 1:
Formula 2:
Formula 3:
Formula 4:
In formula 4, R is various different substituents, the i.e. derivative of small molecule porphyrin, is selected from phenyl, bromophenyl or imidazole radicals.
Cyclic acid anhydride uses succinic anhydride or phthalic anhydride.
Epoxides uses epoxychloropropane, propylene oxide, styrene oxide or 7-oxa-bicyclo[4.1.0.
Solvent is using at least one of tetrahydrofuran, toluene and dimethylformamide.
Synthetic method of the present invention is using epoxides and cyclic acid anhydride as monomer, under conditions of drying, anaerobic, by no metal
Catalyst initiated polymerization, it is post-treated to obtain aliphatic polyester；
Have many advantages, such as no metal residual, high catalytic efficiency, the good, high yield of selectivity and narrow molecular weight distribution；With very high
Practical application value.Catalytic efficiency is up to 726.19g polymer/g catalyst in synthesis process, in the copolymer of synthesis
Amount of polyester is more than 90%.
Detailed description of the invention
Fig. 1 be the embodiment of the present invention 1 prepare fatty acid polyester nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure；
Fig. 2 be the embodiment of the present invention 2 prepare fatty acid polyester nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure；
Fig. 3 be the embodiment of the present invention 3 prepare fatty acid polyester nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure；
Fig. 4 be the embodiment of the present invention 4 prepare fatty acid polyester nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure；
Fig. 5 be the embodiment of the present invention 5 prepare fatty acid polyester nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure；
Fig. 6 be the embodiment of the present invention 6 prepare fatty acid polyester nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure；
Fig. 7 be the embodiment of the present invention 7 prepare fatty acid polyester nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure；
Fig. 8 be the embodiment of the present invention 8 prepare fatty acid polyester nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure；
Fig. 9 be the embodiment of the present invention 9 prepare fatty acid polyester nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure；
Figure 10 be the embodiment of the present invention 10 prepare fatty acid polyester nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure；
Figure 11 be the embodiment of the present invention 11 prepare fatty acid polyester nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure；
Figure 12 be the embodiment of the present invention 12 prepare fatty acid polyester nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure；
Figure 13 be the embodiment of the present invention 13 prepare fatty acid polyester nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure；
Figure 14 be the embodiment of the present invention 14 prepare fatty acid polyester nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure；
Figure 15 be the embodiment of the present invention 15 prepare fatty acid polyester nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure；
Figure 16 be comparative example 1 verify the reaction product after catalyst and epoxide reaction nucleus magnetic hydrogen spectrum (1HNMR, CDCl3)
Figure；
Figure 17 be 2 catalyst of comparative example reacted with succinic anhydride after reaction product nucleus magnetic hydrogen spectrum (1HNMR, CDCl3) figure.
Specific embodiment
The present invention will be further described in the following with reference to the drawings and specific embodiments.
Embodiment 1
It weighs in 0.01g TPP catalyst and 3.84g succinic anhydride merging reaction flask, vacuumizes；By 3mL epoxychloropropane with
3mL n,N-Dimethylformamide sequentially adds in reaction flask, is warming up to 80 DEG C, heats 10h, then cools to room temperature；It will polymerization
Object is dissolved out from reaction flask with chloroform, and using n-hexane as sedimentation agent, settle out product, is placed in a vacuum drying oven 80 DEG C of vacuum
It is dry, fatty acid polyester 7.57g is obtained, amount of polyester is 94% in the fatty acid polyester.
Embodiment 2
It weighs in 0.01g TPP catalyst and 4.28g succinic anhydride merging reaction flask, vacuumizes displaced air；By 3mL epoxy third
Alkane and 3mL n,N-Dimethylformamide are squeezed into reaction flask, are warming up to 80 DEG C, are heated 10h, are then cooled to room temperature；It will polymerization
Object is dissolved out from reaction flask with chloroform, using n-hexane as sedimentation agent, after the product that settles out, is placed in a vacuum drying oven 80 DEG C very
Sky is dry, obtains fatty acid polyester 4.96g, and amount of polyester is 60% in the fatty acid polyester.
Embodiment 3
It weighs in 0.01g TPP catalyst and 2.63g succinic anhydride merging reaction flask, vacuumizes displaced air；By 3mL Oxybenzene
Ethylene and 3mL n,N-Dimethylformamide are squeezed into reaction flask, are warming up to 80 DEG C, are heated 10h, are then cooled to room temperature；It will gather
It closes object to be dissolved out from reaction flask with chloroform, using n-hexane as sedimentation agent, after the product that settles out, is placed in a vacuum drying oven 80 DEG C
Vacuum drying, obtains fatty acid polyester 5.23g, and amount of polyester is 90% in the fatty acid polyester.
Embodiment 4
It weighs in 0.01g TPP catalyst and 2.95g succinic anhydride merging reaction flask, vacuumizes displaced air；By 3mL epoxide ring
Hexane and 3mL n,N-Dimethylformamide are squeezed into reaction flask, are warming up to 80 DEG C, are heated 10h, are then cooled to room temperature；It will gather
It closes object to be dissolved out from reaction flask with chloroform, using n-hexane as sedimentation agent, after the product that settles out, is placed in a vacuum drying oven 80 DEG C
Vacuum drying, obtains fatty acid polyester 5.03g, and amount of polyester is 85% in the fatty acid polyester.
Embodiment 5
It weighs in 0.01g TPP catalyst and 5.67g phthalic anhydride merging reaction flask, vacuumizes displaced air；By 3mL ring
Oxygen chloropropane and 3mL n,N-Dimethylformamide are squeezed into reaction flask, are warming up to 80 DEG C, are heated 10h, are then cooled to room temperature；
Polymer is dissolved out from reaction flask with chloroform, using n-hexane as sedimentation agent, after the product that settles out, is placed in a vacuum drying oven
80 DEG C of vacuum drying, obtain fatty acid polyester 9.01g, and amount of polyester is 97% in the fatty acid polyester.
Embodiment 6
It weighs in 0.01g TBPP catalyst and 3.84g succinic anhydride merging reaction flask, vacuumizes displaced air；By 3mL epoxy
Chloropropane and 3mL n,N-Dimethylformamide are squeezed into reaction flask, are warming up to 80 DEG C, are heated 10h, are then cooled to room temperature；It will
Polymer is dissolved out from reaction flask with chloroform, and using n-hexane as sedimentation agent, settle out product, is placed in a vacuum drying oven 80 DEG C
Vacuum drying, obtains fatty acid polyester 7.26g, and amount of polyester is 93% in the fatty acid polyester.
Embodiment 7
Title goes 0.01g TBPP catalyst and 4.28g succinic anhydride to be placed in reaction flask, vacuumizes displaced air；By 3mL epoxy
Propane and 3mL n,N-Dimethylformamide are squeezed into reaction flask, are warming up to 80 DEG C, are heated 10h, are then cooled to room temperature；It will gather
It closes object to be dissolved out from reaction flask with chloroform, using n-hexane as sedimentation agent, settle out product, is placed in a vacuum drying oven 80 DEG C very
Sky is dry, obtains fatty acid polyester 6.45g, and amount of polyester is 86% in the fatty acid polyester.
Embodiment 8
It weighs in 0.01g TBPP catalyst and 2.63g succinic anhydride merging reaction flask, vacuumizes displaced air；3mL is aoxidized
Styrene and 3mL n,N-Dimethylformamide are squeezed into reaction flask, are warming up to 80 DEG C, are heated 10h, are then cooled to room temperature；It will
Polymer is dissolved out from reaction flask with chloroform, using n-hexane as sedimentation agent, after the product that settles out, is placed in a vacuum drying oven 80
DEG C vacuum drying, obtain fatty acid polyester 5.49g, in the fatty acid polyester amount of polyester be 94%.
Embodiment 9
It weighs in 0.01g TBPP catalyst and 2.95g succinic anhydride merging reaction flask, vacuumizes displaced air；By 3mL epoxy
Hexamethylene and 3mL n,N-Dimethylformamide are squeezed into reaction flask, are warming up to 80 DEG C, are heated 10h, are then cooled to room temperature；It will
Polymer is dissolved out from reaction flask with chloroform, using n-hexane as sedimentation agent, after the product that settles out, is placed in a vacuum drying oven 80
DEG C vacuum drying, obtain fatty acid polyester 5.83g, in the fatty acid polyester amount of polyester be 99%.
Embodiment 10
It weighs in 0.01g TBPP catalyst and 5.67g phthalic anhydride merging reaction flask, vacuumizes displaced air；By 3mL
Epoxychloropropane and 3mL n,N-Dimethylformamide are squeezed into reaction flask, are warming up to 80 DEG C, are heated 10h, are subsequently cooled to room
Temperature；Polymer is dissolved out from reaction flask with chloroform, using n-hexane as sedimentation agent, after the product that settles out, is placed in vacuum drying
80 DEG C of vacuum drying, obtain fatty acid polyester 8.62g in case, and amount of polyester is 94% in the fatty acid polyester.
Embodiment 11
It weighs in 0.01g TImp catalyst and 3.84g succinic anhydride merging reaction flask, vacuumizes displaced air；By 3mL epoxy
Chloropropane and 3mL n,N-Dimethylformamide are squeezed into reaction flask, are warming up to 80 DEG C, are heated 10h, are then cooled to room temperature；It will
Polymer is dissolved out from reaction flask with chloroform, and using n-hexane as sedimentation agent, settle out product, is placed in a vacuum drying oven 80 DEG C
Vacuum drying, obtains fatty acid polyester 7.04g, and amount of polyester is 90% in the fatty acid polyester.
Embodiment 12
It weighs in 0.01g TImp catalyst and 4.28g succinic anhydride merging reaction flask, vacuumizes displaced air；By 3mL epoxy
Propane and 3mL n,N-Dimethylformamide are squeezed into reaction flask, are warming up to 80 DEG C, are heated 10h, are then cooled to room temperature；It will gather
It closes object to be dissolved out from reaction flask with chloroform, using n-hexane as sedimentation agent, settle out product, is placed in a vacuum drying oven 80 DEG C very
Sky is dry, obtains fatty acid polyester 5.58g, and amount of polyester is 57% in the fatty acid polyester.
Embodiment 13
It weighs in 0.01g TImp catalyst and 2.63g succinic anhydride merging reaction flask, vacuumizes displaced air；3mL is aoxidized
Styrene and 3mL n,N-Dimethylformamide are squeezed into reaction flask, are warming up to 80 DEG C, are heated 10h, are then cooled to room temperature；It will
Polymer is dissolved out from reaction flask with chloroform, using n-hexane as sedimentation agent, after the product that settles out, is placed in a vacuum drying oven 80
DEG C vacuum drying, obtain fatty acid polyester 5.40g, in the fatty acid polyester amount of polyester be 93%.
Embodiment 14
It weighs in 0.01g TImp catalyst and 2.95g succinic anhydride merging reaction flask, vacuumizes displaced air；By 3mL epoxy
Hexamethylene and 3mL n,N-Dimethylformamide are squeezed into reaction flask, are warming up to 80 DEG C, are heated 10h, are then cooled to room temperature；It will
Polymer is dissolved out from reaction flask with chloroform, using n-hexane as sedimentation agent, after the product that settles out, is placed in a vacuum drying oven 80
DEG C vacuum drying, obtain fatty acid polyester 5.30g, in the fatty acid polyester amount of polyester be 90%.
Embodiment 15
It weighs in 0.01g TImp catalyst and 5.67g phthalic anhydride merging reaction flask, vacuumizes displaced air；By 3mL
Epoxychloropropane and 3mL n,N-Dimethylformamide are squeezed into reaction flask, are warming up to 80 DEG C, are heated 10h, are subsequently cooled to room
Temperature；Polymer is dissolved out from reaction flask with chloroform, using n-hexane as sedimentation agent, after the product that settles out, is placed in vacuum drying
80 DEG C of vacuum drying, obtain fatty acid polyester 6.05g in case, and amount of polyester is 66% in the fatty acid polyester.
Embodiment 1, embodiment 6 and embodiment 11 are using epoxychloropropane and succinic anhydride as reaction monomers synthetic fat
Fat acid polyester, the nuclear-magnetism figure of fatty acid polyester obtained in three embodiments, such as Fig. 1 (embodiment 1), Fig. 6 (embodiment 6) and
(abscissa is chemical shift, unit: ppm in figure) shown in Figure 11 (embodiment 11), it can be seen from the figure that fatty acid obtained
Chemical shift 5.0~the 5.5ppm and 4.0~4.4ppm of polyester correspond respectively to-CH- and-CH in ester chain2The absorption of upper proton
Peak, 1.0~1.5ppm of chemical shift are-CH in ester chain3The absorption peak of proton, 3.4~3.7ppm of chemical shift are polyether chain
In-CH- and-CH2The absorption peak of upper proton, 2.61ppm are the characteristic absorption peak of proton in polyester chain succinic anhydride, illustrate this
Invention synthetic method successfully synthesizes the polymer of epoxychloropropane and succinic anhydride.
Embodiment 2, embodiment 7 and embodiment 12 are using propylene oxide and succinic anhydride as reaction monomers synthctic fat
Acid polyester, the nuclear-magnetism figure of fatty acid polyester obtained in three embodiments, such as Fig. 2 (embodiment 2), Fig. 7 (embodiment 7) and figure
12(embodiment 12) shown (abscissa is chemical shift, unit: ppm in figure).It can be seen from the figure that the change of fatty acid polyester
1.0~1.3ppm of displacement study is-CH in PO polyether chain3The absorption peak of upper proton, 5.0~5.5ppm of chemical shift and 4.0~
4.4ppm corresponds respectively to-CH- and-CH in ester chain2The absorption peak of upper proton, 1.0~1.5ppm of chemical shift be ester chain in-
CH3The absorption peak of proton, 3.4~3.7ppm of chemical shift are-CH- and-CH in polyether chain2The absorption peak of upper proton,
2.61ppm is the characteristic absorption peak of proton in polyester chain succinic anhydride, thus proves the rouge using synthetic method of the present invention synthesis
The link configuration of fat acid polyester is made of the autohemagglutination chain link of acid anhydrides and epoxides alternating copolymerization chain link and a small amount of epoxides.
Embodiment 3, embodiment 8 and embodiment 13 are using styrene oxide and succinic anhydride as reaction monomers synthetic fat
Fat acid polyester, the nuclear-magnetism figure of fatty acid polyester obtained in three embodiments, such as Fig. 3 (embodiment 3), Fig. 8 (embodiment 8) and
(abscissa is chemical shift, unit: ppm in figure) shown in Figure 13 (embodiment 13).It can be seen from the figure that fatty acid polyester
Chemical shift 4.7~5.0ppm and 4.0~4.4ppm correspond respectively to-CH- and-CH in ester chain2The absorption peak of upper proton is changed
7.0~7.5ppm of displacement study is the absorption peak of proton on phenyl ring in ester chain, and 3.4~3.7ppm of chemical shift is-CH- in polyether chain
With-CH2The absorption peak of upper proton, 2.61ppm are the characteristic absorption peak of proton in polyester chain succinic anhydride, thus prove to use
The link configuration of the fatty acid polyester of synthetic method of the present invention synthesis is by acid anhydrides and epoxides alternating copolymerization chain link and a small amount of
The autohemagglutination chain link of epoxides forms.
Embodiment 4, embodiment 9 and embodiment 14 are using 7-oxa-bicyclo[4.1.0 and succinic anhydride as reaction monomers synthetic fat
Fat acid polyester, the nuclear-magnetism figure of fatty acid polyester obtained in three embodiments, such as Fig. 4 (embodiment 4), Fig. 9 (embodiment 9) and
(abscissa is chemical shift, unit: ppm in figure) shown in Figure 14 (embodiment 14).It can be seen from the figure that fatty acid polyester
4.5~5.0ppm of chemical shift, corresponds respectively to the absorption peak of the upper proton of-CH- in ester chain, and 1.2~1.7ppm of chemical shift is
- CH in ester chain2The absorption peak of proton, 3.4~3.7ppm of chemical shift are-CH- and-CH in polyether chain2The absorption of upper proton
Peak, 2.61ppm are the characteristic absorption peak of proton in polyester chain succinic anhydride, are thus proved using synthetic method of the present invention synthesis
The link configuration of fatty acid polyester is by the autohemagglutination link set of acid anhydrides and epoxides alternating copolymerization chain link and a small amount of epoxides
At.
Embodiment 5, embodiment 10 and embodiment 15 are using epoxychloropropane and phthalic anhydride as reaction monomers
Synthctic fat acid polyester, the nuclear-magnetism figure of fatty acid polyester obtained in three embodiments, as Fig. 5 (embodiment 5), Figure 10 are (real
Apply example 10) and Figure 15 (embodiment 15) shown (abscissa is chemical shift, unit: ppm in figure).It can be seen from the figure that system
Chemical shift 5.0~the 5.5ppm and 4.0~4.4ppm of the fatty acid polyester obtained correspond respectively to-CH- and-CH in ester chain2On
The absorption peak of proton, 1.0~1.5ppm of chemical shift are-CH in ester chain3The absorption peak of proton, 3.4~3.7ppm of chemical shift
For-CH- in polyether chain and-CH2The absorption peak of upper proton, 7.5~7.8ppm are the spy of proton in polyester chain phthalic anhydride
Absorption peak is levied, illustrates that synthetic method of the present invention successfully synthesizes the polymer of epoxychloropropane and phthalic anhydride.
Comparative example 1
It weighs in 0.005g TBPP catalyst merging reaction flask, vacuumizes displaced air；By 1.5mL propylene oxide and 1.5mL
N,N-Dimethylformamide is squeezed into reaction flask, is stirred for 24 hours at room temperature, is obtained reaction product.
Reaction product made from comparative example 1 is dissolved in CDCl3In, carry out nucleus magnetic hydrogen spectrum test.
Comparative example 2
It weighs in 0.005g TBPP catalyst and 2.14g succinic anhydride merging reaction flask, vacuumizes displaced air；By 3mL N,
Dinethylformamide is squeezed into reaction flask, is stirred for 24 hours at room temperature, is obtained reaction product.
Reaction product made from comparative example 2 is dissolved in CDCl3In, carry out nucleus magnetic hydrogen spectrum test.
Synthetic method of the present invention is using small molecule Porphyrin and its derivative as a kind of non-metal catalyst catalysis epoxidation object
It is due to upper in the pyrroles's nitrogen that contains in small molecule Porphyrin and its derivative with cyclic acid anhydride copolymerization aliphatic polyester
The oxygen of active hydrogen and epoxides is readily formed hydrogen bond, makees probing into for mechanism, as shown in figure 16, epoxides by taking TBPP as an example
Peak be subjected to displacement, so that activating epoxides promotes its open loop.And its small molecule Porphyrin and its derivative can not activate
Acid anhydrides promotes its open loop, and as shown in figure 17, therefore, after epoxides open loop forms reactive intermediate, acid anhydrides is constantly inserted into shape
At aliphatic polyester.
Claims (5)
1. a kind of method of non-metal catalyst catalysis epoxidation object and cyclic acid anhydride copolymerization aliphatic polyester, feature exist
In the synthetic method specifically:
1 ︰ 200~400 in mass ratio takes non-metal catalyst and cyclic acid anhydride respectively, then by dissolution 1g in 300mL solvent without gold
The ratio of metal catalyst takes solvent, then takes volume epoxides identical with solvent volume；By non-metal catalyst and ring-type acid
Acid anhydride is placed in a reaction flask, and is vacuumized, and epoxides and solvent are sequentially added in the reaction flask, and it is 80 that reaction flask, which is placed in temperature,
8~20h is heated in~130 DEG C of environment, is cooled to room temperature, polymer is dissolved out from reaction flask with chloroform, with n-hexane
It for sedimentation agent, after the product that settles out, is dried in vacuo at a temperature of 80~100 DEG C, aliphatic polyester is made.
2. non-metal catalyst catalysis epoxidation object as described in claim 1 and cyclic acid anhydride copolymerization aliphatic polyester
Method, which is characterized in that the non-metal catalyst uses small molecule Porphyrin and its derivative, comprising: tetraphenylporphyrin CAS
Number: 917-23-7；5,10,15,20- tetra- (4- bromophenyl) porphyrins, No. CAS: 29162-73-0；meso- four [4(or 5)-imidazoles
Base] porphyrin.
3. non-metal catalyst catalysis epoxidation object as described in claim 1 and cyclic acid anhydride copolymerization aliphatic polyester
Method, which is characterized in that the cyclic acid anhydride uses succinic anhydride or phthalic anhydride.
4. non-metal catalyst catalysis epoxidation object as described in claim 1 and cyclic acid anhydride copolymerization aliphatic polyester
Method, which is characterized in that the epoxides uses epoxychloropropane, propylene oxide, 7-oxa-bicyclo[4.1.0 or styrene oxide.
5. non-metal catalyst catalysis epoxidation object as described in claim 1 and cyclic acid anhydride copolymerization aliphatic polyester
Method, which is characterized in that the solvent is using at least one of tetrahydrofuran, toluene and dimethylformamide.
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| CN112574405A (en) * | 2020-12-18 | 2021-03-30 | 西北师范大学 | Method for synthesizing block polyester by heterogeneous zinc carboxylate catalytic mixed monomer |
| CN113087884A (en) * | 2021-05-27 | 2021-07-09 | 天津大学 | Method for preparing poly (butylene succinate) |
| CN113185679A (en) * | 2021-05-27 | 2021-07-30 | 天津大学 | Preparation method of polyether ester |
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| CN112574405B (en) * | 2020-12-18 | 2022-07-12 | 西北师范大学 | Method for synthesizing block polyester by heterogeneous zinc carboxylate catalytic mixed monomer |
| CN113087884A (en) * | 2021-05-27 | 2021-07-09 | 天津大学 | Method for preparing poly (butylene succinate) |
| CN113185679A (en) * | 2021-05-27 | 2021-07-30 | 天津大学 | Preparation method of polyether ester |
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