CN1687176A - Method for preparing aliphatic polyester - Google Patents
Method for preparing aliphatic polyester Download PDFInfo
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- CN1687176A CN1687176A CN 200510050265 CN200510050265A CN1687176A CN 1687176 A CN1687176 A CN 1687176A CN 200510050265 CN200510050265 CN 200510050265 CN 200510050265 A CN200510050265 A CN 200510050265A CN 1687176 A CN1687176 A CN 1687176A
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Abstract
The present invention discloses a preparation method of aliphatic polyester. It is characterized by that under the condition of inert atmosphere the cyclic ester monomer, metal-free N-heterocyctic carbene catalyst and alcoholic compound are uniformly mixed according to the mole ratio of 1:0.0002-0.2:0.0002-0.2 and reacted for 5 min to 24 hr at zero deg.C-150 deg.C so as to obtain the aliphatic polyester.
Description
Technical field
The present invention relates to macromolecular material, relate in particular to a kind of preparation method of aliphatic polyester
Background technology
Most of macromolecular materials that use such as polyolefine, polystyrene, polyvinyl chloride etc. are difficult to natural degradation at occurring in nature at present, their waste has caused serious pollution to environment, and the what is called " white pollution " that particularly disposable daily plastic brings is badly in need of finding terms of settlement.Aliphatic polyester is there is ester bond in a class on its macromolecular main chain an aliphatics macromolecular material, under water, enzyme or other microbial process, the ester bond on the macromolecular main chain ruptures, and molecular weight reduces gradually, generate the small molecules product, thereby be the macromolecular material that a class can be degraded fully.If use Biodegradable Polymers to replace macromolecular materials such as polyolefine commonly used,, avoided above-mentioned environmental problem owing to after reaching its work-ing life, can be degraded into the small molecules product of toxicological harmless fully.Aliphatic polyester not only has biodegradable, also has excellent biological compatibility, does not have tangible toxicity and rejection with the living organism of living, and medical materials such as alternative existing metal, pottery and natural polymer are used for the bio-medical field.When reaching its work-ing life, its nontoxic degraded product can participate in the human body metabolic process, thereby is absorbed and excretes, and the problem of having avoided second operation to take out can be widely used in fields such as surgical implant, medicine sustained release and organizational project.
Aliphatic polyester is synthesized by ring-opening polymerization by cyclic ester monomers such as corresponding lactone, lactides usually.Ring-opening polymerization catalyst commonly used has stannous octoate, alkoxy aluminum compound, rare earth catalyst etc., new catalyst system is also in continuous appearance, existing lot of documents discloses cyclic ester monomers such as lactone, lactide and has carried out ring-opening polymerization and come the synthesizing biological degradable polymer, for example, United States Patent (USP) 4045418,4057537,3736646,3463158,3620218,3636956,3297033,3284417,3169945,3021309,2890208, Chinese patent CN1164651C, CN1544504A, CN1306019A, CN1175601A etc.But all contain metallic element in the above-mentioned catalyzer, thereby inevitably can more residual metallic elements in its catalysis synthetic polymkeric substance.Studies show that even obtained drugs approved by FDA, most popular stannous octoate catalyst, its tin residual in polymkeric substance also may cause some cytotoxicities, and tin there is very bad influence to child's health.Although there are some nontoxic catalyzer, its catalytic activity is often too low, and polymerization temperature is too high, a little less than the ability of regulation and control to polymer architecture, is difficult to the requirement that reaches practical.The catalytic activity of cyclic ester monomer such as lactone, lactide ring-opening polymerization catalyst and this contradiction between the security are restricting the development of high-quality biodegradable polymer for a long time, are limiting to further expanding of its Application Areas.On the other hand, the active ring-opening polymerization of cyclic ester monomers such as realization lactone, lactide is the molecular weight of controlling polymers and the important means of distribution, sequential structure and product quality thereof.Therefore, research and develop not containing metal element, non-toxic efficient, can realize that the catalyzer of active ring-opening polymerization has very important significance to quality and the application security that improves biodegradable polymer.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of aliphatic polyester.
A kind of preparation method of aliphatic polyester: under inert atmosphere, cyclic ester monomer, metal-less N-heterocyclic carbone catalyst, alcohol compound is even by 1: 0.0002～0.2: 0.0002～0.2 mixed in molar ratio, under 0 ℃～150 ℃ temperature, react 5 minutes to 24 hours, obtain aliphatic polyester.
The preparation method of another kind of aliphatic polyester: under inert atmosphere, cyclic ester monomer, metal-less N-heterocyclic carbone catalyst, alcohol compound and organic solvent are pressed 1: 0.0002～0.2: 0.0002～0.2: the mixed in molar ratio of 0.1-100 is even, under 0 ℃～150 ℃ temperature, reacted 5 minutes to 24 hours, the polymers soln that obtains precipitates with precipitation agent, after filtration, washing, vacuum-drying, obtain aliphatic polyester.
Cyclic ester monomer described in the present invention is selected from: glycollide, rac-Lactide, beta-propiolactone, beta-butyrolactone, gamma-butyrolactone, γ-Wu Neizhi, δ-Wu Neizhi, 6-caprolactone, 1,4-dioxy hexane-2-one, 1, any one or its mixture in 5-dioxy heptane-2-ketone.
The general structure of the metal-less N-heterocyclic carbone catalyst described in the present invention is:
Wherein, R
1, R
3Be selected from H atom, C
1～C
20Alkyl, C
3～C
20Branched-chain alkyl, C
5～C
12Cycloalkyl, substituted cycloalkyl, C
1～C
6In thiazolinyl, aryl, substituted aryl, the aralkyl any one; R
4, R
5Be selected from H atom, fluorine atom, Cl atom, Br atom, cyano group, C
1-C
6In the alkyl any one.
Alcohol compound described in the present invention is selected from: methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, Pentyl alcohol, n-hexyl alcohol, n-Octanol, nonylcarbinol, lauryl alcohol, positive hexadecanol, Virahol, isopropylcarbinol, the 2-enanthol, sec-n-octyl alcohol, 2-ethyl-1-hexanol, ethylene glycol, glycol ether, 1, ammediol, 1, the 2-propylene glycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, neopentyl glycol, 1, the 6-hexylene glycol, 1, the 4-cyclohexanedimethanol, glycerine, tetramethylolmethane, 1,1, the 1-TriMethylolPropane(TMP), Xylitol, sorbyl alcohol, phenylcarbinol, phenylethyl alcohol, hexalin, end hydroxy polyether, in the hydroxyl telechelic polyester any one or its mixture.
Organic solvent described in the present invention is selected from tetrahydrofuran (THF), hexanaphthene, hexane, heptane, octane, benzene,toluene,xylene, chloroform, methylene dichloride, ether, acetone, butanone, pimelinketone, dioxane, N, any one or its mixture in dinethylformamide, dimethyl sulfoxide (DMSO), the phenyl ether.
The polymkeric substance that the preparation method of the aliphatic polyester that the present invention proposes has the catalytic activity height, rate of polymerization is fast, polymerization time is short, polymerization temperature is low, molecular weight distribution is narrow, polymericular weight is controlled, rate of polymerization and polymericular weight can be regulated and control relatively independently, obtain is advantage such as containing metal element not, is expected to improve simultaneously the quality and the application security of polymkeric substance.
Description of drawings
Fig. 1 is 1, the molecular weight distribution curve of the poly-epsilon-caprolactone that the carbene catalyzed 6-caprolactone ring-opening polymerization of 3-di-n-butyl imidazoles obtains.
Fig. 2 is 1, and the number-average molecular weight of the poly-epsilon-caprolactone that the carbene catalyzed 6-caprolactone ring-opening polymerization of 3-di-n-butyl imidazoles obtains and polydispersity index are with the variation of monomer conversion.
Embodiment
The body ring-opening polymerization preparation method who the invention provides a kind of aliphatic polyester is as follows: under inert atmosphere, metal-less N-heterocyclic carbone catalyst, the alcohol compound of cyclic ester monomer, on-site preparation is even by 1: 0.0002～0.2: 0.0002～0.2 mixed in molar ratio, under 0 ℃～150 ℃ temperature, react 5 minutes to 24 hours, obtain aliphatic polyester.
The present invention also provides a kind of solution ring-opening polymerization preparation method of aliphatic polyester as follows: under inert atmosphere, metal-less N-heterocyclic carbone catalyst, alcohol compound and the organic solvent of cyclic ester monomer, on-site preparation are pressed 1: 0.0002～0.2: 0.0002～0.2: the mixed in molar ratio of 0.1-100 is even, under 0 ℃～150 ℃ temperature, reacted 5 minutes to 24 hours, the polymers soln that obtains precipitates with precipitation agent, after filtration, washing, vacuum-drying, obtain aliphatic polyester.
Among the preparation method of aliphatic polyester provided by the invention, described cyclic ester monomer is selected from: glycollide, rac-Lactide, beta-propiolactone, beta-butyrolactone, gamma-butyrolactone, γ-Wu Neizhi, δ-Wu Neizhi, 6-caprolactone, 1,4-dioxy hexane-2-one, 1, any one or its mixture in 5-dioxy heptane-2-ketone.
Among the preparation method of aliphatic polyester provided by the invention, described cyclic ester monomer preferentially is selected from glycollide, rac-Lactide, beta-butyrolactone, δ-Wu Neizhi, 6-caprolactone, 1,4-dioxy hexane-2-one, 1, any one or its mixture in 5-dioxy heptane-2-ketone.
Among the preparation method of aliphatic polyester provided by the invention, the general structure of described metal-less N-heterocyclic carbone catalyst is:
Wherein, R
1, R
3Be selected from H atom, C
1～C
20Alkyl, C
3～C
20Branched-chain alkyl, C
5～C
12Cycloalkyl, substituted cycloalkyl, C
1～C
6In thiazolinyl, aryl, substituted aryl, the aralkyl any one; R
4, R
5Be selected from H atom, fluorine atom, Cl atom, Br atom, cyano group, C
1-C
6In the alkyl any one.
R in the general structure of metal-less N-heterocyclic carbone catalyst among the present invention
1, R
3Be selected from H atom, methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, sec.-propyl, isobutyl-, isopentyl, isohexyl, the tertiary butyl, vinyl, allyl group, alkene butyl, phenyl, benzyl, 4-aminomethyl phenyl, 2,6-3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropyl phenyl, 2,4, any one in the 6-triisopropyl phenyl; R
4, R
5Be selected from H atom, F atom, Cl atom, Br atom, cyano group, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, n-pentyl, the n-hexyl any one.
R in the general structure of no metal metal-less N-heterocyclic carbone catalyst among the present invention
1, R
3Preferentially be selected from methyl, ethyl, normal-butyl, n-hexyl, n-octyl, sec.-propyl, vinyl, allyl group, phenyl, 2,6-3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 2, any one in the 6-diisopropyl phenyl; R
4, R
5Preferentially be selected from H atom, Cl atom, Br atom, cyano group, methyl, ethyl, butyl, the hexyl any one.
Metal-less N-heterocyclic carbone catalyst real-world effectiveness preparation under protection of inert gas such as nitrogen, argon gas among the present invention by substituted imidazole salt and metallic compound; promptly; it in the mol ratio that replaces imidazole salts metallizing thing 1: 0.001～1: 2 ratio; substituted imidazole salt and metallic compound are mixed; reaction obtained to 10 hours in 1 minute after filtration under 0 ℃～100 ℃ temperature.
Metal-less N-heterocyclic carbone catalyst also can be by substituted imidazole salt among the present invention; metallic compound and organic solvent are at nitrogen; real-world effectiveness preparation under the protection of inert gas such as argon gas; promptly; metallic compound is dissolved in obtains solution of metal compound in the organic solvent; be 1: 0.001～1: 2 ratio adding substituted imidazole salt then in the mol ratio that replaces imidazole salts metallizing thing; be that 1: 0.001～1: 2 ratio joins in the organic solvent in the mol ratio that replaces imidazole salts metallizing thing perhaps with metallic compound and substituted imidazole salt; stirring mixes it; under 0 ℃～100 ℃ temperature; reacted 1 minute to 10 hours; filter, obtain catalyst solution.
Among the present invention, the general structure of the substituted imidazole salt of preparation metal-less N-heterocyclic carbone catalyst is:
Wherein, R
1, R
3Be selected from H atom, C
1～C
20Alkyl, C
3～C
20Branched-chain alkyl, C
5～C
12Cycloalkyl, substituted cycloalkyl, C
1～C
6In thiazolinyl, aryl, substituted aryl, the aralkyl any one; R
4, R
5Be selected from H atom, fluorine atom, Cl atom, Br atom, cyano group, C
1-C
6In the alkyl any one; Y
-Be to be selected from following negatively charged ion: Cl
-, Br
-, I
-, BF
4 -, PF
6 -, CF
3SO
3 -, (CF
3SO
2)
2N
-, NO
3 -, SO
4 2-, CH
3COO
-, CF
3COO
-, CH
3C
6H
5COO
-, SCN
-In any one.
Among the present invention in the general structure of substituted imidazole salt of preparation metal-less N-heterocyclic carbone catalyst, R
1, R
3Preferentially be selected from methyl, ethyl, normal-butyl, n-hexyl, n-octyl, sec.-propyl, vinyl, allyl group, phenyl, 2,6-3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 2, any one in the 6-diisopropyl phenyl; R
4, R
5Be selected from H atom, F atom, Cl atom, Br atom, cyano group, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, n-pentyl, the n-hexyl any one.Y
-Preferentially be selected from following negatively charged ion: Cl
-, Br
-, BF
4 -, PF
6 -, CF
3SO
3 -, NO
3 -, SO
4 2-, CH
3COO
-In any one.
The metallic compound of preparation metal-less N-heterocyclic carbone catalyst is selected from any one or its mixture in potassium tert.-butoxide, sodium tert-butoxide, lithium hydride, sodium hydride, potassium hydride KH, the hydrolith among the present invention.
The organic solvent of preparation metal-less N-heterocyclic carbone catalyst is selected from tetrahydrofuran (THF), hexanaphthene, hexane, heptane, octane, benzene,toluene,xylene, chloroform, methylene dichloride, ether, acetone, butanone, pimelinketone, dioxane, N among the present invention, any one or its mixture in the organic solvents such as dinethylformamide, dimethyl sulfoxide (DMSO).
The temperature of reaction of preparation metal-less N-heterocyclic carbone catalyst is preferably 20 ℃～60 ℃ among the present invention, and the reaction times is preferably 5 minutes to 1 hour.
Among the preparation method of aliphatic polyester provided by the invention, described alcohol compound is selected from: methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, Pentyl alcohol, n-hexyl alcohol, n-Octanol, nonylcarbinol, lauryl alcohol, positive hexadecanol, Virahol, isopropylcarbinol, the 2-enanthol, sec-n-octyl alcohol, 2-ethyl-1-hexanol, ethylene glycol, glycol ether, 1, ammediol, 1, the 2-propylene glycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, neopentyl glycol, 1, the 6-hexylene glycol, 1, the 4-cyclohexanedimethanol, glycerine, tetramethylolmethane, 1,1, the 1-TriMethylolPropane(TMP), Xylitol, sorbyl alcohol, phenylcarbinol, phenylethyl alcohol, hexalin, end hydroxy polyether, in the hydroxyl telechelic polyester any one or its mixture.
Among the preparation method of aliphatic polyester provided by the invention, described alcohol compound preferentially is selected from: ethanol, propyl carbinol, n-hexyl alcohol, n-Octanol, lauryl alcohol, positive hexadecanol, Virahol, 2-ethyl-1-hexanol, ethylene glycol, glycol ether, 1, ammediol, 1,4-butyleneglycol, neopentyl glycol, 1,6-hexylene glycol, glycerine, tetramethylolmethane, 1,1, any one or its mixture in 1-TriMethylolPropane(TMP), Xylitol, sorbyl alcohol, phenylcarbinol, phenylethyl alcohol, hexalin, end hydroxy polyether, the hydroxyl telechelic polyester.
Among the preparation method of aliphatic polyester provided by the invention, described organic solvent is selected from tetrahydrofuran (THF), hexanaphthene, hexane, heptane, octane, benzene,toluene,xylene, chloroform, methylene dichloride, ether, acetone, butanone, pimelinketone, dioxane, N, any one or its mixture in dinethylformamide, dimethyl sulfoxide (DMSO), the phenyl ether.
Among the preparation method of aliphatic polyester provided by the invention, described organic solvent preferentially is selected from any one or its mixture in tetrahydrofuran (THF), hexanaphthene, hexane, toluene, chloroform, methylene dichloride, ether, acetone, the dioxane.
Among the preparation method of aliphatic polyester provided by the invention, the mol ratio of described cyclic ester monomer, metal-less N-heterocyclic carbone catalyst, alcohol compound is preferably 1: 0.0005～and 0.05: 0.0005～0.05.
Among the preparation method of aliphatic polyester provided by the invention, the mol ratio of described cyclic ester monomer, metal-less N-heterocyclic carbone catalyst, alcohol compound more preferably is 1: 0.001～0.05: 0.001～0.05.
Among the preparation method of aliphatic polyester provided by the invention, described range of reaction temperature is 0 ℃～150 ℃, preferred 10 ℃～120 ℃, and especially preferred 20 ℃～100 ℃.
Among the preparation method of aliphatic polyester provided by the invention, metal-less N-heterocyclic carbone catalyst shows very high catalytic activity, and catalytic polymerization efficiently just at normal temperatures is reflected at the transformation efficiency that can reach more than 90% in 5 minutes to 5 hours.
Among the preparation method of aliphatic polyester provided by the invention, polyreaction has the living polymerization feature, and the resulting polymers molecular weight increases and linear the increase with monomer conversion, narrow molecular weight distribution, and rate of polymerization and polymericular weight can be controlled relatively independently.The polymer molecule weight range can be regulated between 500～500000, and the polymericular weight polydispersity index is 1.1～2.0.
The polymkeric substance that the preparation method of aliphatic polyester provided by the invention has the catalytic activity height, rate of polymerization is fast, polymerization time is short, polymerization temperature is low, molecular weight distribution is narrow, polymericular weight is controlled, rate of polymerization and polymericular weight can be regulated and control relatively independently, obtain is advantage such as containing metal element not, is expected to improve simultaneously the quality and the application security of polymkeric substance.
The embodiment that the invention is further illustrated by the following examples, but be not limited to these embodiment.
Embodiment 1:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; with 1; 3-dibutyl imidazolium bromide (bbimBr) 26mg (0.1mmol) and potassium tert.-butoxide 10mg (0.09mmol) mix; fully reacted 20 minutes down at 25 ℃; generate 1; 3-di-n-butyl imidazoles Cabbeen (bbim) catalyzer adds monomer 6-caprolactone 1ml (9.4mmol) and initiator phenylcarbinol 10.8mg (0.1mmol) then, stirs it is mixed.After 30 minutes, add terminator water termination reaction in reaction under 25 ℃.Add 10ml tetrahydrofuran (THF) dissolving resulting polymers, after precipitation, filtration and drying, obtain poly-epsilon-caprolactone.Monomer conversion is 99.2%.Recording its number-average molecular weight with GPC is 9960, and polydispersity index is 1.39.The molecular weight distribution curve of poly-epsilon-caprolactone is seen Fig. 1.
Embodiment 2:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; potassium tert.-butoxide 10mg (0.09mmol) is dissolved in the 2ml tetrahydrofuran (THF); add substituted imidazole salt 1 then; 3-dibutyl imidazolium bromide (bbimBr) 26mg (0.1mmol); stirring mixes it, reacts 20 minutes down at 25 ℃, filters; obtain 1,3-di-n-butyl imidazoles Cabbeen (bbim) catalyst solution.Add monomer 6-caprolactone 1ml (9.4mmol), tetrahydrofuran (THF) 5ml, initiator phenylcarbinol 10.8mg (0.1mmol) then, stirring mixes it.After 30 minutes, add terminator water termination reaction in reaction under 25 ℃.Resulting polymers solution obtains poly-epsilon-caprolactone after precipitation, filtration and drying.Monomer conversion is 95.3%.Recording its number-average molecular weight with GPC is 8960, and polydispersity index is 1.34.
Embodiment 3:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; potassium tert.-butoxide 10mg (0.09mmol) is dissolved in the 2ml tetrahydrofuran (THF); add substituted imidazole salt 1 then; 3-dibutyl imidazolium bromide (bbimBr) 26mg (0.1mmol); stirring mixes it, reacts 20 minutes down at 25 ℃, filters; obtain 1,3-di-n-butyl imidazoles Cabbeen (bbim) catalyst solution.Add monomer δ-Wu Neizhi 1ml (10mmol) and initiator phenylcarbinol 10.8mg (0.1mmol) then, stirring mixes it.After 45 minutes, add terminator water termination reaction in reaction under 25 ℃.Add tetrahydrofuran (THF) 5ml dissolving resulting polymers solution, polymers soln obtains poly-δ-Wu Neizhi after precipitation, filtration and drying.Monomer conversion is 78.5%.Recording its number-average molecular weight with GPC is 9980, and polydispersity index is 1.50.
Embodiment 4:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; potassium tert.-butoxide 10mg (0.09mmol) is dissolved in the 2ml tetrahydrofuran (THF); add substituted imidazole salt 1-normal-butyl-3-Methylimidazole bromide (bmimBr) 21.8mg (0.1mmol) then; stirring mixes it; reacted 20 minutes down at 25 ℃; filter; obtain 1-normal-butyl-3-Methylimidazole Cabbeen (bmim) catalyst solution; add monomer 6-caprolactone 1ml (9.4mmol) and initiator phenylcarbinol 10.8mg (0.1mmol) then, stirring mixes it.After 30 minutes, add terminator water termination reaction in reaction under 25 ℃.In resulting polymers solution, add the 5ml tetrahydrofuran (THF) and carry out dissolved dilution, after precipitation, filtration and drying, obtain poly-epsilon-caprolactone.Monomer conversion is 85.8%.Recording its number-average molecular weight with GPC is 7180, and polydispersity index is 1.50.
Embodiment 5:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; potassium tert.-butoxide 10mg (0.09mmol) is dissolved in the 2ml tetrahydrofuran (THF); add substituted imidazole salt 1-n-hexyl-3-Methylimidazole bromide (hmimBr) 24.6mg (0.1mmol) then; stirring mixes it; fully reacted 20 minutes down at 25 ℃, generate 1-n-hexyl-3-Methylimidazole Cabbeen (hmim) catalyst solution.Add monomer 6-caprolactone 1ml (9.4mmol), initiator phenylcarbinol 10.8mg (0.1mmol), tetrahydrofuran (THF) 50ml (684mmol) then, stirring mixes it.After 5 minutes, add terminator water termination reaction in reaction under 25 ℃.Resulting polymers solution obtains poly-epsilon-caprolactone after precipitation, filtration and drying.Monomer conversion is 100%.Recording its number-average molecular weight with GPC is 10240, and polydispersity index is 2.37.
Embodiment 6:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; in the 2ml tetrahydrofuran (THF), add substituted imidazole salt 1-normal-butyl-3-Methylimidazole bromide (bmimBr) 21.8mg (0.1mmol) and tetracol phenixin 46mg (0.3mmol); reacted 30 minutes down at 20 ℃; solvents tetrahydrofurane and unreacted tetracol phenixin are removed in underpressure distillation then; obtain substituted imidazole salt 1-normal-butyl-3-methyl-4,5-dichloro-imidazole bromide (Cl
2BmimBr).Add potassium tert.-butoxide 5mg (0.09mmol) and 2ml tetrahydrofuran (THF) then, stirring mixes it, reacts 20 minutes down at 25 ℃, filters, and obtains 1-normal-butyl-3-Methylimidazole Cabbeen (bmim) catalyst solution.Add monomer 6-caprolactone 1ml (9.4mmol), initiator phenylcarbinol 10.8mg (0.1mmol), tetrahydrofuran (THF) 50ml then, stirring mixes it.After 2 hours, add terminator water termination reaction in reaction under 25 ℃.Resulting polymers solution obtains poly-epsilon-caprolactone after precipitation, filtration and drying.Monomer conversion is 83.2.％。Recording its number-average molecular weight with GPC is 9840, and polydispersity index is 1.42.
Embodiment 7:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; potassium tert.-butoxide 10mg (0.09mmol) is dissolved in the 2ml tetrahydrofuran (THF); add substituted imidazole salt 1 then; 3-dibutyl imidazolium bromide (bbimBr) 26mg (0.1mmol); stirring mixes it, reacts 20 minutes down at 25 ℃, filters; obtain 1,3-di-n-butyl imidazoles Cabbeen (bbim) catalyst solution.Add monomer 6-caprolactone 1.5ml (14.1mmol) and initiator ethylene glycol 6.2mg (0.1mmol) then, stirring mixes it.After 30 minutes, add terminator water termination reaction in reaction under 25 ℃.Add tetrahydrofuran (THF) 5ml dissolved dilution resulting polymers solution, polymers soln obtains poly-epsilon-caprolactone after precipitation, filtration and drying.Monomer conversion is 88.5%.Recording its number-average molecular weight with GPC is 14300, and polydispersity index is 1.32.
Embodiment 8:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; potassium tert.-butoxide 10mg (0.09mmol) is dissolved in the 2ml tetrahydrofuran (THF); add substituted imidazole salt 1 then; 3-dibutyl imidazolium bromide (bbimBr) 26mg (0.1mmol); stirring mixes it, reacts 20 minutes down at 25 ℃, filters; obtain 1,3-di-n-butyl imidazoles Cabbeen (bbim) catalyst solution.Add monomer 6-caprolactone 1.5ml (14.1mmol) and initiator 1,1 then, 1-TriMethylolPropane(TMP) 13.4mg (0.1mmol), stirring mixes it.After 45 minutes, add terminator water termination reaction in reaction under 25 ℃.Add tetrahydrofuran (THF) 5ml dissolved dilution resulting polymers solution, polymers soln obtains poly-epsilon-caprolactone after precipitation, filtration and drying.Monomer conversion is 86.8%.Recording its number-average molecular weight with GPC is 15200, and polydispersity index is 1.46.
Embodiment 9:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; potassium tert.-butoxide 10mg (0.09mmol) is dissolved in the 2ml tetrahydrofuran (THF); add substituted imidazole salt 1 then; 3-dibutyl imidazolium bromide (bbimBr) 26mg (0.1mmol); stirring mixes it, reacts 20 minutes down at 25 ℃, filters; obtain 1,3-di-n-butyl imidazoles Cabbeen (bbim) catalyst solution.Add monomer 6-caprolactone 1.5ml (14.1mmol) and molecular weight then and be 2000 terminal hydroxy group polyoxyethylene glycol (PEG2000) 200mg (0.1mmol), stir it is mixed.After 45 minutes, add terminator water termination reaction in reaction under 25 ℃.Add tetrahydrofuran (THF) 5ml dissolved dilution resulting polymers solution, polymers soln obtains poly-epsilon-caprolactone after precipitation, filtration and drying.Monomer conversion is 86.8%.Recording its number-average molecular weight with GPC is 15200, and polydispersity index is 1.46.
Embodiment 10:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; potassium tert.-butoxide 10mg (0.09mmol) is dissolved in the 2ml tetrahydrofuran (THF); add substituted imidazole salt 1 then; 3-dibutyl imidazolium bromide (bbimBr) 26mg (0.1mmol); stirring mixes it, reacts 20 minutes down at 25 ℃, filters; obtain 1,3-di-n-butyl imidazoles Cabbeen (bbim) catalyst solution.Add monomer 6-caprolactone 53ml (0.5mol) and phenylcarbinol 108mg (1mmol) then, stirring mixes it.After 24 hours, add terminator water termination reaction in reaction under 25 ℃.Add tetrahydrofuran (THF) 500ml dissolved dilution resulting polymers solution, polymers soln obtains poly-epsilon-caprolactone after precipitation, filtration and drying.Monomer conversion is 75.3%.Recording its number-average molecular weight with GPC is 45200, and polydispersity index is 1.32.
Embodiment 11:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; potassium tert.-butoxide 200mg (1.8mmol) is dissolved in the 2ml tetrahydrofuran (THF); add substituted imidazole salt 1 then; 3-dibutyl imidazolium bromide (bbimBr) 520mg (2mmol); stirring mixes it, reacts 20 minutes down at 25 ℃, filters; obtain 1,3-di-n-butyl imidazoles Cabbeen (bbim) catalyst solution.Add monomer 6-caprolactone 53ml (0.5mol) and phenylcarbinol 10.8mg (0.1mmol) then, stirring mixes it.After 24 hours, add terminator water termination reaction in reaction under 25 ℃.Add tetrahydrofuran (THF) 500ml dissolved dilution resulting polymers solution, polymers soln obtains poly-epsilon-caprolactone after precipitation, filtration and drying.Monomer conversion is 65.3%.Recording its number-average molecular weight with GPC is 75200, and polydispersity index is 2.23.
Embodiment 12:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; with 1; 3-dibutyl imidazolium bromide (bbimBr) 26mg (0.1mmol) and potassium tert.-butoxide 10mg (0.09mmol) mix; fully reacted 20 minutes down at 25 ℃; generate 1; 3-di-n-butyl imidazoles Cabbeen (bbim) catalyzer adds monomer 6-caprolactone 1ml (9.4mmok) and initiator phenylcarbinol 10.8mg (0.1mmol) then, stirs it is mixed.After 15 minutes, add terminator water termination reaction in reaction under 150 ℃.Add 10ml tetrahydrofuran (THF) dissolving resulting polymers, after precipitation, filtration and drying, obtain poly-epsilon-caprolactone.Monomer conversion is 91.2%.Recording its number-average molecular weight with GPC is 9260, and polydispersity index is 1.35.
Embodiment 13:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; potassium tert.-butoxide 10mg (0.09mmol) is dissolved in the 2ml tetrahydrofuran (THF); add substituted imidazole salt 1 then; 3-dibutyl imidazolium bromide (bbimBr) 26mg (0.1mmol); stirring mixes it, reacts 20 minutes down at 25 ℃, filters; obtain 1,3-di-n-butyl imidazoles Cabbeen (bbim) catalyst solution.Add monomer 6-caprolactone 1ml (9.4mmol), tetrahydrofuran (THF) 5ml, initiator phenylcarbinol 10.8mg (0.1mmol) then, stirring mixes it.After 2 hours, add terminator water termination reaction in reaction under 0 ℃.Resulting polymers solution obtains poly-epsilon-caprolactone after precipitation, filtration and drying.Monomer conversion is 87.3%.Recording its number-average molecular weight with GPC is 9150, and polydispersity index is 1.31.
Embodiment 14:
Carry out one group of experiment that polymerization reaction time is different under the condition identical with embodiment 2, the reaction times was respectively 10 minutes, 20 minutes, 23 minutes, 26 minutes, 30 minutes, 50 minutes, 70 minutes.Monomer conversion is respectively 34.0%, 46.8%, 54.3%, 55.8%, 64.1%, 80.5%, 98.5%, the polymkeric substance number-average molecular weight is respectively 3850,5500,5990,6310,7200,9260,12200, and polydispersity index is respectively 1.10,1.17,1.20,1.23,1.28,1.29,1.31 (see figure 2)s.
Claims (9)
1, a kind of preparation method of aliphatic polyester, it is characterized in that: under inert atmosphere, cyclic ester monomer, metal-less N-heterocyclic carbone catalyst, alcohol compound is even by 1: 0.0002～0.2: 0.0002～0.2 mixed in molar ratio, under 0 ℃～150 ℃ temperature, react 5 minutes to 24 hours, obtain aliphatic polyester.
2, the preparation method of a kind of aliphatic polyester as claimed in claim 1, it is characterized in that described cyclic ester monomer is selected from: glycollide, rac-Lactide, beta-propiolactone, beta-butyrolactone, gamma-butyrolactone, γ-Wu Neizhi, δ-Wu Neizhi, 6-caprolactone, 1,4-dioxy hexane-2-one, 1, any one or its mixture in 5-dioxy heptane-2-ketone.
3, the preparation method of a kind of aliphatic polyester as claimed in claim 1 is characterized in that the general structure of described metal-less N-heterocyclic carbone catalyst is:
Wherein, R
1, R
3Be selected from H atom, C
1～C
20Alkyl, C
3～C
20Branched-chain alkyl, C
5～C
12Cycloalkyl, substituted cycloalkyl, C
1～C
6In thiazolinyl, aryl, substituted aryl, the aralkyl any one; R
4, R
5Be selected from H atom, fluorine atom, Cl atom, Br atom, cyano group, C
1-C
6In the alkyl any one.
4, the preparation method of a kind of aliphatic polyester as claimed in claim 1, it is characterized in that described alcohol compound is selected from: methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, Pentyl alcohol, n-hexyl alcohol, n-Octanol, nonylcarbinol, lauryl alcohol, positive hexadecanol, Virahol, isopropylcarbinol, the 2-enanthol, sec-n-octyl alcohol, 2-ethyl-1-hexanol, ethylene glycol, glycol ether, 1, ammediol, 1, the 2-propylene glycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, neopentyl glycol, 1, the 6-hexylene glycol, 1, the 4-cyclohexanedimethanol, glycerine, tetramethylolmethane, 1,1, the 1-TriMethylolPropane(TMP), Xylitol, sorbyl alcohol, phenylcarbinol, phenylethyl alcohol, hexalin, end hydroxy polyether, in the hydroxyl telechelic polyester any one or its mixture.
5, a kind of preparation method of aliphatic polyester, it is characterized in that: under inert atmosphere, cyclic ester monomer, metal-less N-heterocyclic carbone catalyst, alcohol compound and organic solvent are pressed 1: 0.0002～0.2: 0.0002～0.2: the mixed in molar ratio of 0.1-100 is even, under 0 ℃～150 ℃ temperature, reacted 5 minutes to 24 hours, the polymers soln that obtains precipitates with precipitation agent, after filtration, washing, vacuum-drying, obtains aliphatic polyester.
6, the preparation method of a kind of aliphatic polyester as claimed in claim 5, it is characterized in that described cyclic ester monomer is selected from: glycollide, rac-Lactide, beta-propiolactone, beta-butyrolactone, gamma-butyrolactone, γ-Wu Neizhi, δ-Wu Neizhi, 6-caprolactone, 1,4-dioxy hexane-2-one, 1, any one or its mixture in 5-dioxy heptane-2-ketone.
7, the preparation method of a kind of aliphatic polyester as claimed in claim 5 is characterized in that the general structure of described metal-less N-heterocyclic carbone catalyst is:
Wherein, R
1, R
3Be selected from H atom, C
1～C
20Alkyl, C
3～C
20Branched-chain alkyl, C
5～C
12Cycloalkyl, substituted cycloalkyl, C
1～C
6In thiazolinyl, aryl, substituted aryl, the aralkyl any one; R
4, R
5Be selected from H atom, fluorine atom, Cl atom, Br atom, cyano group, C
1-C
6In the alkyl any one.
8, the preparation method of a kind of aliphatic polyester as claimed in claim 5, it is characterized in that described alcohol compound is selected from: methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, Pentyl alcohol, n-hexyl alcohol, n-Octanol, nonylcarbinol, lauryl alcohol, positive hexadecanol, Virahol, isopropylcarbinol, the 2-enanthol, sec-n-octyl alcohol, 2-ethyl-1-hexanol, ethylene glycol, glycol ether, 1, ammediol, 1, the 2-propylene glycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, neopentyl glycol, 1, the 6-hexylene glycol, 1, the 4-cyclohexanedimethanol, glycerine, tetramethylolmethane, 1,1, the 1-TriMethylolPropane(TMP), Xylitol, sorbyl alcohol, phenylcarbinol, phenylethyl alcohol, hexalin, end hydroxy polyether, in the hydroxyl telechelic polyester any one or its mixture.
9, the preparation method of a kind of aliphatic polyester as claimed in claim 5, it is characterized in that described organic solvent is selected from tetrahydrofuran (THF), hexanaphthene, hexane, heptane, octane, benzene,toluene,xylene, chloroform, methylene dichloride, ether, acetone, butanone, pimelinketone, dioxane, N, any one or its mixture in dinethylformamide, dimethyl sulfoxide (DMSO), the phenyl ether.
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