CN101200462A - Ring aliphatic carbonate monomer, polymer and preparation method thereof - Google Patents
Ring aliphatic carbonate monomer, polymer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a cyclic aliphatic carbonate monomer including 2'-benzyloxygenamide trimethylene carbonate and 2-methyl-2-benzyloxygenamide trimethylene carbonate and the polymer and the preparation method thereof. The raw material for the preparation of the two monomers is 2-amino-1,3-propanediol and 2-methyl-2-amino-1,3-propanediol, the amino group is protected, and the hydroxyl group at two ends and ethyl cacodylic acid chloroformate react to produce the monomer. The polymer with the amino at the protective side is obtained by the homopolymerization of the monomer or the copolymerization of the monomer and the aliphatic cyclic ester, and then the polymer with the side amino is obtained after escaping the protection of the polymer. The functional side amino of the polymer can be loaded with the drug molecules and the bioactive peptide by the covalent bond and the ionic bond. Thereby the invention can be applied in the fields of the drug controlled release, the gene therapy and the tissue engineering.
Description
Technical field
The present invention relates to annular aliphatic carbonate monomer, its polymkeric substance and preparation method, belong to biomedical materials field.
Background technology
In recent decades, along with advancing by leaps and bounds of developing rapidly of polymer science and modern pharmacy, biology and engineering science, the research of biological medical polymer material has obtained developing rapidly.Wherein Biodegradable Polymers can be in vivo be degraded to the small molecules product gradually through the process of hydrolysis or enzymolysis, finally excrete by normal process of physiological metabolism, therefore do not need second operation to take out after implanting, thereby become the research focus and emphasis in biomedical polymer field.Obtained widespread use in operating sutures, artificial skin, artificial blood vessel, the fixing fields such as reparation and medicine sustained release that reach of bone.At present, the biodegradable synthetic macromolecule of mainly studying and using mainly comprises aliphatic polyester, polyamino acid, poly phosphate, poly-acid anhydrides, poe, polycarbonate etc.These are high molecular synthetic mainly synthetic by the method for polycondensation and ring-opening polymerization.The macromolecular material of easier acquisition high molecular of ring-opening polymerization and superior performance and obtain using more widely wherein.Coming the cyclic monomer of composite structure novelty by molecular designing is one of important channel that further develops Biodegradable Polymers.
Wherein aliphatic polycarbonate is that polymer can fall/absorb in the important biology of a class.It has excellent biological compatibility and physical and mechanical properties, can satisfy different needs.On the other hand, polycarbonate degraded back generates carbonic acid gas and neutral dibasic alcohol, the caused ill effect of carboxylic-acid substance that can avoid poly(lactic acid), polyglycolic acid etc. to produce in degradation process.Therefore, the biodegradable polycarbonate has obtained application more and more widely at aspects such as medicine sustained release, material implanted, organizational projects.Recently, the research of introducing functional group on the molecular chain of polymkeric substance is particularly active, because it is significant in practice to have the polymkeric substance of functional group.For example, on these functional groups, connect various medicines and form the polymer prodrug, can realize that the position-controllable of medicine discharges or lasting release; Connect molecule such as antibody and polysaccharide, can make polymkeric substance and micella thereof, capsule have target function with target function; Connection has the active molecule of other biological, can improve the biocompatibility and the biological activity of material; By the introducing of functional group can also change polymkeric substance degradation rate, physical and mechanical properties, hydrophilic and hydrophobic can etc., thereby have the research of aliphatic polyester of functional group and the very big interest that application has caused people.
The function side group mainly comprises carboxyl (COOH), amino (NH
2), hydroxyl (OH) and sulfydryl (SH) etc.Wanting the polymkeric substance of anamorphic zone function side group, generally is the monomer that first anamorphic zone has functional group, carries out polymerization or copolymerization then.
At this on the one hand, (disclosed the synthetic method of 5-benzyloxy-trimethylene carbonate as Chinese patent CN1323795A, Chinese patent CN1335330A has disclosed poly-(5-benzyloxy-trimethylene carbonate) and preparation method thereof and purposes to disclose a plurality of patents.Chinese patent CN1746207 has disclosed aliphatic carbonic acid ester polymer and the synthetic method and the purposes of band side carboxyl.Chinese patent CN1803884 has disclosed based on the aliphatic carbonic acid ester polymer of the band pendant hydroxyl group of tetramethylolmethane and synthetic method and purposes).With these hydroxyls that can react, carboxyl, polymkeric substance and medicine or other biological active substance can be got up by covalent bonds, form the polymer drug system, perhaps pass through further modification, improve the performances such as wetting ability, biocompatibility and biological degradation of polymkeric substance, to satisfy different needs.In the bibliographical information, the research of introducing function amino on the side chain of polyester is less relatively but up to the present.Last century the nineties, people such as the Langer of the U.S. introduce the morpholine diketone monomer of Methionin and LA copolymerization amino.It is too low that but the shortcoming of this method maximum is exactly a productive rate, cause introducing on the polymkeric substance amino molar content and almost can not surpass 10% (Barrera D.A., Zylstra E., Lansbury P.T., Langer R.Synthesis and RGD peptide modification of a newbiodegradable copolymer:poly (lactic acid-co-lysine) J.Am.Chem.Soc.1993; 115:11010).The Endo of Japan etc. has reported to be six-ring amino-carbon acid esters (the Matsuo J. of three kinds of similar of raw material synthetic with amino acid, Aoki K., Sanda F., Endo T.Substituent Effecton the Anionic Equilibrium Polymerization of Six-Membered Cyclic Carbonates.Macromolecules 1998; 31:4432-4438), but their synthetic route more complicated, reactions steps is more.
Summary of the invention
In order to satisfy the demand of bio-medical material, solve the shortcoming and defect that above-mentioned polymkeric substance exists, the present invention at first provides two kinds of annular aliphatic carbonate monomers: 2-benzyloxy amide group trimethylene carbonate or 2-methyl-2-benzyloxy amide group trimethylene carbonate, their structural formula are respectively (A) and (B):
The present invention also provides above-mentioned 2-benzyloxy amide group trimethylene carbonate (A) and 2-methyl-monomeric preparation method of 2-benzyloxy amide group trimethylene carbonate (B), and concrete synthetic route is as follows:
The preparation process and the condition of monomer (A) are as follows: raw material 2-amino-1, it is in 10% the aqueous sodium carbonate that ammediol is dissolved in mass concentration, be made into the solution of mass concentration 2～10%, add 1 then, 4-dioxane, the volume ratio of aqueous sodium carbonate and dioxane are 2: 1～1: 1, after fully mixing, under the temperature of ice-water bath, add 2-amino-1, the chloroformic acid benzyl ester that the ammediol molar weight is 1～2 times, room temperature reaction 8～20h with constant pressure funnel, with ethyl acetate extraction three times, organic layer with anhydrous magnesium sulfate drying after, rotary evaporation concentrates, and uses re-crystallizing in ethyl acetate again, obtain 2-benzyloxy amide group-1, ammediol; Be catalyzer with triethylamine again, tetrahydrofuran (THF) is made solvent, under-10 ℃～30 ℃ the condition, and 2-benzyloxy amide group-1, the Vinyl chloroformate reaction of ammediol and its 1～3 times of molar weight, the reaction times is 2～24h, obtains 2-benzyloxy amide group trimethylene carbonate.
The preparation method of monomer (B): its reactions steps is identical with the preparation method of described monomer (A) with condition, just with raw material by 2-amino-1, ammediol changes 2-methyl-2-amino-1, ammediol into.
Institute's synthetic monomer (A) and (B), its structure be through infrared spectra (FT-IR), proton NMR spectrum (
1H NMR), and carbon-13 nmr (
13C NMR) confirms.
Institute's synthetic monomer (A) and (B) is to contain the amino six-ring cyclic carbonate of protection, can carry out homopolymerization, also can carry out copolymerization.
The invention provides the multipolymer of the arbitrary proportion of the homopolymer of above-mentioned annular aliphatic carbonate monomer or annular aliphatic carbonate monomer and aliphatics cyclic ester, be characterized in having on the molecular chain side amino.Wherein annular aliphatic carbonate is monomer (A) and monomer (B), the aliphatics cyclic ester for the aliphatics cyclic ester monomer be rac-Lactide, glycollide and 6-caprolactone a kind of, two or three, ratio is not limit.
The present invention also provides the preparation method of homopolymer or the annular aliphatic carbonate monomer and the aliphatics cyclic ester multipolymer of above-mentioned annular aliphatic carbonate monomer, comprises following two steps:
The first step is a catalyzer with the zinc ethyl, and with annular aliphatic carbonate monomer, or the mixture of annular aliphatic carbonate monomer and aliphatics cyclic ester monomer carries out polymerization; Wherein monomer and catalyst molar ratio are 50～1000: 1, and polymerization temperature is 100～180 ℃, and polymerization time is 12～72h;
Described annular aliphatic carbonate monomer is 2-benzyloxy amide group trimethylene carbonate (A) or 2-methyl-2-benzyloxy amide group trimethylene carbonate (B);
Described aliphatics cyclic ester monomer be rac-Lactide, glycollide and 6-caprolactone a kind of, two or three, ratio is not limit;
The mol ratio of described annular aliphatic carbonate monomer and aliphatics cyclic ester monomer is any ratio, but the content of annular aliphatic carbonate monomer is non-vanishing;
Second step, the amino polymkeric substance of above-mentioned band protection is carried out deprotection, adopt the method for following deprotection:
(1) hydrogen bromide hydrolysis method: will be dissolved in the methylene dichloride with the amino polymkeric substance of protection earlier, be made into the solution of mass concentration 10～20%, after the ice-water bath cooling, adding and the isopyknic volumetric concentration of methylene dichloride are 25% HBr/HAc, under 0 ℃ of condition, and stirring reaction 10～30min, by the rotary evaporation concentrated reaction mixture, use the cold diethyl ether sedimentation then, filter and collect, drying at room temperature is to constant weight; Perhaps,
(2) hydrogenating reduction method: will be dissolved in tetrahydrofuran (THF) and the methanol mixed solvent with the amino polymkeric substance of protection; the volume ratio 9/1 to 1/9 of tetrahydrofuran (THF) and methyl alcohol wherein; be made into the solution of mass concentration 10～20%; feed hydrogen; hydrogen pressure is 0.8～1.2MPa, and temperature of reaction is 20～60 ℃, and catalyzer is palladium/carbon or palladium hydroxide/carbon; wherein palladium or palladium hydroxide mass content 5～20%; palladium/carbon or palladium hydroxide/carbon and the mol ratio 1～100% of waiting to remove benzyl, stirring reaction 24～72h, elimination insolubles; mixed solvent washing with tetrahydrofuran (THF) and methyl alcohol; concentrate, use the methyl alcohol sedimentation, filter; washing, vacuum-drying.
More than band is amino, or the amino polycarbonate of protection, or the multipolymer of annular aliphatic carbonate and aliphatics cyclic ester can both biological degradation, has good biocompatibility.The introducing of functional group can change physics, the chemistry and biology character of polycarbonate, and the existence of functional side amino can also realize being written into of drug molecule, bioactive peptide by covalent linkage, ionic linkage.Therefore can obtain practical application in fields such as medicine sustained release, gene therapy and organizational projects.
Description of drawings
Embodiment
Embodiment 1:2-benzyloxy amide group-1, ammediol synthetic
Get 10g (0.11mol) 2-amino-1, it is in 10% the aqueous sodium carbonate that ammediol is dissolved in the 250ml mass concentration, add 125ml 1 then, the 4-dioxane, after fully mixing, under the condition of ice-water bath, slowly add 15.7ml (0.11mol) chloroformic acid benzyl ester with constant pressure funnel, behind the room temperature reaction 8h, add the 50ml distilled water diluting earlier, use ethyl acetate extraction again three times, the organic layer anhydrous magnesium sulfate drying is after rotary evaporation concentrates, use re-crystallizing in ethyl acetate, obtain 20g 2-benzyloxy amide group-1, ammediol, productive rate 80%.
Embodiment 2:2-benzyloxy amide group-1, ammediol synthetic
Get 10g (0.11mol) 2-amino-1, it is in 10% the aqueous sodium carbonate that ammediol is dissolved in the 250ml mass concentration, add 250ml 1 then, the 4-dioxane, after fully mixing, under the condition of ice-water bath, slowly add 31.4ml (0.22mol) chloroformic acid benzyl ester with constant pressure funnel, behind the room temperature reaction 8h, add the 50ml distilled water diluting earlier, use ethyl acetate extraction again three times, the organic layer anhydrous magnesium sulfate drying is after rotary evaporation concentrates, use re-crystallizing in ethyl acetate, obtain 20.8g 2-benzyloxy amide group-1, ammediol, productive rate 84%.
Embodiment 3:2-methyl-2-benzyloxy amide group-1, ammediol synthetic
Get 10g (0.095mol) 2 methyl-2-amino-1, it is in 10% the aqueous sodium carbonate that ammediol is dissolved in the 250ml mass concentration, add 200ml 1 then, the 4-dioxane, after fully mixing, under the condition of ice-water bath, slowly add 21ml (0.14mol) chloroformic acid benzyl ester with constant pressure funnel, behind the room temperature reaction 8h, add the 50ml distilled water diluting earlier, use ethyl acetate extraction again three times, the organic layer anhydrous magnesium sulfate drying is after rotary evaporation concentrates, use re-crystallizing in ethyl acetate, obtain 17.7g2-methyl-2-benzyloxy amide group-1, ammediol, productive rate 78%.
The preparation of embodiment 4:2-benzyloxy amide group trimethylene carbonate
With 10g (0.044mol) 2-benzyloxy amide group-1, ammediol and 4.2ml (0.044mol) Vinyl chloroformate is dissolved in the 200ml tetrahydrofuran (THF), under 0 ℃ of condition, slowly add 6ml (0.044mol) triethylamine, room temperature reaction 2h filters out the triethylamine salt of generation, filtrate decompression concentrates, with tetrahydrofuran (THF)/ether recrystallization, obtain white crystal, i.e. 2-benzyloxy amide group trimethylene carbonate.Productive rate 49%.Its
1H NMR spectrogram is seen accompanying drawing 1.
The preparation of embodiment 5:2-benzyloxy amide group trimethylene carbonate
With 10g (0.044mol) 2-benzyloxy amide group-1, ammediol and 7.9ml (0.08mol) Vinyl chloroformate is dissolved in the 400ml tetrahydrofuran (THF), under 0 ℃ of condition, slowly add 12ml (0.086mol) triethylamine, room temperature reaction 12h filters out the triethylamine salt of generation, filtrate decompression concentrates, with tetrahydrofuran (THF)/ether recrystallization, obtain white crystal, i.e. 2-benzyloxy amide group trimethylene carbonate.Productive rate 65%.
The preparation of embodiment 6:2-methyl-2-benzyloxy amide group trimethylene carbonate
With 10g (0.042mol) 2-methyl-2-benzyloxy amide group-1, ammediol and 4.0ml (0.04mol) Vinyl chloroformate is dissolved in the 200ml tetrahydrofuran (THF), under 0 ℃ of condition, slowly add 6ml (0.043mol) triethylamine, room temperature reaction 2h filters out the triethylamine hydrochloride of generation, and filtrate decompression concentrates, with tetrahydrofuran (THF)/ether recrystallization, obtain 2-methyl-2-benzyloxy amide group trimethylene carbonate.Productive rate 40%.
The preparation of embodiment 7:2-methyl-2-benzyloxy amide group trimethylene carbonate
With 10g (0.042mol) 2-methyl-2-benzyloxy amide group-1, ammediol and 6ml (0.063mol) Vinyl chloroformate is dissolved in the 300ml tetrahydrofuran (THF), under 0 ℃ of condition, slowly add 8ml (0.057mol) triethylamine, room temperature reaction 8h filters out the triethylamine hydrochloride of generation, filtrate decompression concentrates, with tetrahydrofuran (THF)/ether recrystallization, obtain white crystal, i.e. 2-methyl-2-benzyloxy amide group trimethylene carbonate.Productive rate 68%.
Synthesizing of embodiment 8:2-benzyloxy amide group trimethylene carbonate homopolymer
Under the condition of anhydrous and oxygen-free, 1mol carbonate monomer 2-benzyloxy amide group trimethylene carbonate is joined in the polyreaction bottle, the zinc ethyl that adds molar weight again and be monomer 1/200 is as initiator, react 12h down at 100 ℃, product dissolves with trichloromethane, the methyl alcohol sedimentation, filter, washing, vacuum-drying promptly obtains the homopolymer of 2-benzyloxy amide group trimethylene carbonate to constant weight under the room temperature.
Synthesizing of embodiment 9:2-methyl-2-benzyloxy amide group trimethylene carbonate homopolymer
Under the condition of anhydrous and oxygen-free, the preparation of 1mol carbonate monomer 2-methyl-2-benzyloxy amide group trimethylene carbonate is joined in the polyreaction bottle, the zinc ethyl that adds monomer molar amount 1/500 again is as initiator, react 24h down at 140 ℃, product dissolves with trichloromethane, and the methyl alcohol sedimentation is filtered, washing, vacuum-drying is to constant weight under the room temperature.
Synthesizing of embodiment 10:2-methyl-2-benzyloxy amide group trimethylene carbonate homopolymer
Under the condition of anhydrous and oxygen-free, the preparation of 1mol carbonate monomer 2-methyl-2-benzyloxy amide group trimethylene carbonate is joined in the polyreaction bottle, the zinc ethyl that adds monomer molar amount 1/1000 again is as initiator, react 24h down at 180 ℃, product dissolves with trichloromethane, and the methyl alcohol sedimentation is filtered, washing, vacuum-drying is to constant weight under the room temperature.
Embodiment 11: the multipolymer of carbonic ether and rac-Lactide synthetic
Under the condition of anhydrous and oxygen-free, 0.1mol carbonate monomer 2-benzyloxy amide group trimethylene carbonate and 0.9mol lactide monomer are joined in the polyreaction bottle, 1/500 the zinc ethyl that adds the monomer integral molar quantity again is as initiator, react 12h down at 120 ℃, product dissolves with trichloromethane, the methyl alcohol sedimentation, filter, washing, vacuum-drying promptly obtains the multipolymer of carbonic ether and rac-Lactide to constant weight under the room temperature.Its
1H NMR spectrogram is seen accompanying drawing 2.
Embodiment 12: the multipolymer of carbonic ether and 6-caprolactone synthetic
Under the condition of anhydrous and oxygen-free, 0.1mol carbonate monomer 2-methyl-2-benzyloxy amide group trimethylene carbonate and 0.5mol 6-caprolactone monomer are joined in the polyreaction bottle, 1/800 the zinc ethyl that adds the monomer integral molar quantity again is as initiator, react 15h down at 130 ℃, product dissolves with trichloromethane, the methyl alcohol sedimentation, filter, washing, 35 ℃ of following vacuum-dryings promptly obtain the multipolymer of carbonic ether and 6-caprolactone to constant weight.
Embodiment 13: the multipolymer of carbonic ether and rac-Lactide, glycollide synthetic
Under the condition of anhydrous and oxygen-free, 0.1mol carbonate monomer 2-benzyloxy amide group trimethylene carbonate and 0.2mol rac-Lactide, 0.2mol glycolide monomer are joined in the polyreaction bottle, 1/1000 the zinc ethyl that adds the monomer integral molar quantity again is as initiator, react 20h down at 140 ℃, product dissolves with trichloromethane, the methyl alcohol sedimentation, filter, washing, 35 ℃ of following vacuum-dryings promptly obtain the multipolymer of carbonic ether and rac-Lactide, glycollide to constant weight.
Embodiment 14: the deprotection (HBr hydrolysis) of poly-(2-benzyloxy amide group trimethylene carbonate)
The homopolymer of the 0.5g 2-benzyloxy amide group trimethylene carbonate that the present invention is obtained is dissolved in the 5ml methylene dichloride, then with the ice-water bath cooling, adds the HBr/HAc of 5ml 25%.Under 0 ℃ of condition, said mixture is stirred 30min, reconcentration is used a large amount of cold diethyl ether sedimentations then, filters and collects, and drying at room temperature is to constant weight.
Embodiment 15: the deprotection of the multipolymer of carbonic ether and rac-Lactide (hydrogenating reduction method)
With 0.5g embodiment 8 resulting polymer dissolution in 20ml tetrahydrofuran (THF) and methanol mixed solvent (volume ratio is 4 to 1), join in the reactor, the hydro-reduction catalyzer palladium hydroxide/carbon (mass content of palladium hydroxide is 20%) that adds 0.03g again, feed hydrogen, hydrogen pressure is 1.2MPa, in temperature is 60 ℃, reaction 48h.Collect product, filter, and with tetrahydrofuran (THF) and methanol wash,
Use the ether sedimentation, filter, vacuum-drying is to constant weight.Its
1H NMR spectrogram is seen accompanying drawing 3.
Claims (5)
1. annular aliphatic carbonate monomer is characterized in that, this monomer is 2-benzyloxy amide group trimethylene carbonate or 2-methyl-2-benzyloxy amide group trimethylene carbonate, and their structural formula is respectively (A) and (B):
2. the preparation method of 2-benzyloxy amide group trimethylene carbonate (A) according to claim 1, preparation process and condition are as follows: raw material 2-amino-1, it is in 10% the aqueous sodium carbonate that ammediol is dissolved in mass concentration, be made into the solution of mass concentration 2～10%, add 1 then, the 4-dioxane, the volume ratio of aqueous sodium carbonate and dioxane is 2: 1～1: 1, after fully mixing, under the temperature of ice-water bath, add 2-amino-1 with constant pressure funnel, the chloroformic acid benzyl ester that the ammediol molar weight is 1～2 times, room temperature reaction 8～20h, with ethyl acetate extraction three times, organic layer with anhydrous magnesium sulfate drying after, rotary evaporation concentrates, use re-crystallizing in ethyl acetate again, obtain 2-benzyloxy amide group-1, ammediol; Be catalyzer with triethylamine again, tetrahydrofuran (THF) is made solvent, under-10 ℃～30 ℃ the condition, and 2-benzyloxy amide group-1, the Vinyl chloroformate reaction of ammediol and its 1～3 times of molar weight, the reaction times is 2～24h, obtains 2-benzyloxy amide group trimethylene carbonate.
3. the preparation method of the described 2-methyl of claim 1-2-benzyloxy amide group trimethylene carbonate (B), its reactions steps is identical with the preparation method of the described monomer 2-of condition and claim 2 benzyloxy amide group trimethylene carbonate (A), be by 2-amino-1 with raw material, ammediol changes 2-methyl-2-amino-1, ammediol into.
4. the multipolymer of homopolymer of the described annular aliphatic carbonate monomer of claim 1, or annular aliphatic carbonate monomer and aliphatics cyclic ester is characterized in that having side amino on their molecular chain; Wherein annular aliphatic carbonate is monomer 2-benzyloxy amide group trimethylene carbonate (A) or monomer 2-methyl-2-benzyloxy amide group trimethylene carbonate (B), the aliphatics cyclic ester for the aliphatics cyclic ester monomer be rac-Lactide, glycollide and 6-caprolactone a kind of, two or three, ratio is not limit.
5. the preparation method of homopolymer of the described annular aliphatic carbonate monomer of claim 4, or annular aliphatic carbonate monomer and aliphatics cyclic ester multipolymer may further comprise the steps:
The first step is a catalyzer with the zinc ethyl, and with annular aliphatic carbonate monomer, or the mixture of annular aliphatic carbonate monomer and aliphatics cyclic ester monomer carries out polymerization; Wherein monomer and catalyst molar ratio are 50～1000: 1, and polymerization temperature is 100～180 ℃, and polymerization time is 12～72h;
Described annular aliphatic carbonate monomer is 2-benzyloxy amide group trimethylene carbonate (A) or 2-methyl-2-benzyloxy amide group trimethylene carbonate (B);
Described aliphatics cyclic ester monomer be rac-Lactide, glycollide and 6-caprolactone a kind of, two or three, ratio is not limit;
The mol ratio of described annular aliphatic carbonate monomer and aliphatics cyclic ester monomer is any ratio, but the content of annular aliphatic carbonate monomer is non-vanishing;
Second step, the amino polymkeric substance of above-mentioned band protection is carried out deprotection, adopt the method for following deprotection:
(1) hydrogen bromide hydrolysis method: will be dissolved in the methylene dichloride with the amino polymkeric substance of protection earlier, be made into the solution of mass concentration 10～20%, after the ice-water bath cooling, adding and the isopyknic volumetric concentration of methylene dichloride are 25% HBr/HAc, under 0 ℃ of condition, and stirring reaction 10～30min, by the rotary evaporation concentrated reaction mixture, use the cold diethyl ether sedimentation then, filter and collect, drying at room temperature is to constant weight; Perhaps,
(2) hydrogenating reduction method: will be dissolved in tetrahydrofuran (THF) and the methanol mixed solvent with the amino polymkeric substance of protection; the volume ratio 9/1 to 1/9 of tetrahydrofuran (THF) and methyl alcohol wherein; be made into the solution of mass concentration 10～20%; feed hydrogen; hydrogen pressure is 0.8～1.2MPa, and temperature of reaction is 20～60 ℃, and catalyzer is palladium/carbon or palladium hydroxide/carbon; wherein palladium or palladium hydroxide mass content 5～20%; palladium/carbon or palladium hydroxide/carbon and the mol ratio 1～100% of waiting to remove benzyl, stirring reaction 24～72h, elimination insolubles; mixed solvent washing with tetrahydrofuran (THF) and methyl alcohol; concentrate, use the methyl alcohol sedimentation, filter; washing, vacuum-drying.
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Cited By (1)
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|---|---|---|---|---|
| CN106397760A (en) * | 2016-12-16 | 2017-02-15 | 常州南京大学高新技术研究院 | Aliphatic polycarbonate with side chain containing amino group and preparation method of aliphatic polycarbonate |
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| CN106397760A (en) * | 2016-12-16 | 2017-02-15 | 常州南京大学高新技术研究院 | Aliphatic polycarbonate with side chain containing amino group and preparation method of aliphatic polycarbonate |
| CN106397760B (en) * | 2016-12-16 | 2019-02-01 | 常州南京大学高新技术研究院 | A kind of side chain contains fatty poly-ester carbonate of amino and preparation method thereof |
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