CN101759845A - Functionalized polyester and preparation method thereof - Google Patents
Functionalized polyester and preparation method thereof Download PDFInfo
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- CN101759845A CN101759845A CN 201010130905 CN201010130905A CN101759845A CN 101759845 A CN101759845 A CN 101759845A CN 201010130905 CN201010130905 CN 201010130905 CN 201010130905 A CN201010130905 A CN 201010130905A CN 101759845 A CN101759845 A CN 101759845A
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Abstract
The invention provides a functionalized polyester, which is prepared by polymerizing functionalized epoxy compound and functionalized anhydride. Because the functional groups on the functionalized epoxy compound and the functionalized anhydride have sensitivity on changes of pH value, temperature and ionic strength, so the polyester prepared from the epoxy compound and the anhydride with the functional groups has multi-responsiveness, a structural unit contained in the polyester has good biocompatibility, and the polyester is biodegradable due to the existence of ester bonds. The functionalized polyester not only has multi-responsiveness, but also has biocompatibility and biodegradability. The invention also provides a preparation method of the functionalized polyester, the method is operated simply, and the reaction is rapid so as to control preparation process of the polyester well.
Description
Technical field
The present invention relates to the Polymer Synthesizing field, be specifically related to a kind of functionalized polyester and preparation method thereof.
Background technology
With poly-epsilon-caprolactone, polylactide, poly-glycollide, polycarbonate etc. are the aliphatic polyester of representative, because its excellent biological compatibility and mechanical property are subjected to extensive concern at bio-medical and pharmaceutical field.These polyester are at the biodegradable suture line, and fields such as tissue engineering bracket and drug delivery and sustained release have good application prospects.But because its hydrophobicity, hemicrystalline and the rejection that causes with the unsuitable interaction of cells in vivo as inflammation, tissue necrosis and thrombosis etc., are restricted it in a lot of the application.And, because these polyester lack functional group, thereby can not realize multiple functionalization and environment-responsive.
The polymkeric substance that can realize many environment-responsives is called the multiple response polymkeric substance, and this kind polymkeric substance can be right, as temperature, and electric current, photoelectricity, external stimuluss such as pH value and ionic strength are made the special property of quick response.But traditional multiple response polymkeric substance mostly is not biodegradable polyolefin polymers, is restricted on using.
Polyester synthetic with many environment-responsives and good biocompatibility becomes a challenge.Chemical Communication p4411-4413 (2009) has reported that a kind of is catalyst 2-((2-(2-methoxy ethoxy) oxyethyl group) methyl) oxyethane and Succinic anhydried polymerization with the aluminum isopropylate, obtain functionalized polyester by 120 ℃ of mass polymerizations, this functionalized polyester has biodegradability and temperature sensitivity, but realize and the copolymerization ratio of other polymkeric substance difficulty, and the stimuli responsive of environment is too single to external world.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of functionalized polyester originally to have multiple environment-responsive, can stimulate to external world as pH value, temperature, particle intensities etc. are made quick response, and have excellent biological compatibility, and biodegradable, less to the human body toxic side effect.
In order to overcome the above problems, the invention provides a kind of functionalized polyester, it is characterized in that general structure is:
Wherein R is that the fusing point of residue after isopropoxy, the small molecular alcohol dehydrogenation or dehydrogenation is lower than the residue that 120 ℃ polymeric initiator forms;
R
1, R
2For functionalization group inequality, described functionalization group are functionalization group in functionalization epoxy compounds and functionalization pentabasic acid acid anhydride or the hexa-atomic acid anhydrides; Described R
1With R
2Mol ratio be 1: 1;
M=1 or 2;
The number-average molecular weight of described functionalized polyester is 3000～120000; Dispersity is 1.10～1.30.
Preferably, described functionalization epoxy compounds is: 2-((2-methoxy ethoxy) methyl) oxyethane, 2-((2 (2-(2-methoxy ethoxy)) oxyethyl group) methyl) oxyethane, 2-2,5,8,11-four oxygen dodecyl oxyethane, 3-epoxy ethyl methoxypropionic acid, N, N-dimethyl-3-epoxy ethyl methoxyethyl amine or N, N-diethyl-3-epoxy ethyl methoxyethyl amine.
Preferably, described functionalization acid anhydrides is: Succinic anhydried, Pyroglutaric acid, 3-t-butoxycarbonyl amino Pyroglutaric acid, 3-N, N-dimethylamino Pyroglutaric acid or 3-N, N-diethylamino Pyroglutaric acid.
Preferably, described small molecular alcohol is: methyl alcohol, Virahol or ethylene glycol.
Preferably, fusing point is lower than 120 ℃ polymeric initiator and is; Number-average molecular weight is 200～10000 polyoxyethylene glycol or poly glycol monomethyl ether.
A kind of preparation method of functionalized polyester comprises:
A) under anhydrous condition, be that 1: 1 functionalization epoxy compounds mixes with the functionalization acid anhydrides with aluminum isopropylate and mol ratio, obtain mixture;
B) under 100 ℃～150 ℃, heat and stir described mixture 34h～38h, make described mixture polymerization reaction take place, obtain polymkeric substance;
C) with getting filtrate after described polymkeric substance dilution, the filtration, more described filtrate is carried out sedimentation, washing, drying operation and finally obtain functionalized polyester.
Preferably, it is characterized in that step c specifically comprises: c 1), use trichloromethane to dilute the polymkeric substance that described step b) obtains, and filter, remove insolubles, obtain filtrate;
C2), with c2) filtrate that obtains is sedimentation in 1: 6～10: 1 the mixing solutions of ether, normal hexane and ethyl acetate in volume ratio, obtains throw out;
C3), wash described throw out, and, obtain functionalized polyester at 20 ℃～30 ℃ dry 20h～26h down with normal hexane.
Preferably, the mol ratio of described aluminum isopropylate and described functionalization epoxy compounds and functionalization acid anhydrides is 1: 15～750: 15～750.
A kind of preparation method of functionalized polyester comprises:
Under anhydrous condition, it is that 1: 1 functionalization epoxy compounds and functionalization acid anhydrides mixes that small molecular alcohol or fusing point are lower than 120 ℃ polymeric initiator, stannous iso caprylate, mol ratio, obtains mixture;
Under 100 ℃～150 ℃, heat and stir described mixture 34h～38h, make described mixture polymerization reaction take place, obtain polymkeric substance;
With getting filtrate after described polymkeric substance dilution, the filtration, more described filtrate is carried out sedimentation, washing, drying operation and finally obtain functionalized polyester.
Preferably, described small molecular alcohol or fusing point are lower than 120 ℃ polymeric initiator and the mol ratio of described stannous iso caprylate and described functionalization epoxy compounds and functionalization acid anhydrides is 1: 2000～100000: 5～250: 5～250.
The invention provides a kind of functionalized polyester, be to carry out polymerization and a kind of polyester of obtaining by functionalization epoxy compounds and functionalization acid anhydrides, because the existence such as 2-(2-methoxy ethoxy) methyl of the functional group on the functionalization epoxy compounds, 2-(2 (2-(2-methoxy ethoxy)) oxyethyl group) methyl, 2-2,5,8, groups such as 11-four oxygen dodecyls all have very strong temperature, the pH value, ionic strength sensibility, and the functional group figure that has on the functionalization acid anhydrides has the pH value, the susceptibility that ionic strength changes, also just had multiple response so have the epoxy compounds of described functionalization group and polyester that the acid anhydrides polymerization obtains, and the structural unit good biocompatibility that is contained in the polyester, and because the existence of ester bond makes polyester biodegradable.So functionalized polyester provided by the invention had both had multiple response, had biocompatibility and biodegradable again.The present invention also provides a kind of preparation method of functionalized polyester, and this method is simple to operate, and being swift in response can be good at realizing the control of polyester manufacture process.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiments of the invention are described, but should be appreciated that just restriction of these descriptions for further specifying the features and advantages of the present invention rather than patent of the present invention being required.
The invention provides a kind of functionalized polyester, general structure is:
Wherein R is that the fusing point of residue after isopropoxy, the small molecular alcohol dehydrogenation or dehydrogenation is lower than the residue that 120 ℃ polymeric initiator forms;
R1, R2 are that functionalization group inequality, described functionalization group are functionalization epoxide group and functionalization anhydride group; The ratio of described functionalization epoxide group and functionalization anhydride group is 1: 1;
M=1 or 2;
The number-average molecular weight of described functionalized polyester is 3000～120000; Dispersity is 1.10～1.30.
Polyester provided by the invention is the polyester with functionalization group that is obtained behind catalyzed polymerization by functionalization epoxy compounds and functionalization acid anhydrides, and this polyester has good biocompatibility and mechanical property has many environment-responsives simultaneously.Be subjected to as temperature when the invention provides functionalized polyester, electric current, photoelectricity, the compatibility relation of can rapid reaction during external stimuluss such as pH value and ionic strength regulating self and environment, just show and to judge environment of living in fast at inside of human body in bio-medical applications, tangible change can take place in the various character of himself, can exist with solid, solution or the form that is adsorbed in carrier surface, reduces the occurrence probability of rejection.
According to R of the present invention is the negatively charged ion that catalyzer or initiator form, for example sec.-propyl oxygen the moon (bear) ion of being decomposed to form of aluminum isopropylate or sec.-propyl oxygen the moon (bearing) ion of dehydrogenation of isopropanol formation, methyl oxygen the moon (bearing) ion that methyl alcohol drags hydrogen evolution, hydroxyethyl oxygen the moon (bearing) ion that ethylene glycol takes off a hydrogen evolution, low-molecular-weight polyoxyethylene glycol the moon (bearing) ion of sloughing a hydrogen evolution or poly glycol monomethyl ether the moon (bearing) ion of sloughing a hydrogen evolution.These negatively charged ion at first make the acid anhydrides open loop, the moon that forms after the acid anhydrides open loop (bearing) ion energy and can only make the open loop of epoxy compounds, and the moon (bearing) ion that open loop of epoxy compound forms makes the acid anhydrides open loop again, carries out chainpropagation by this alternately mode of ring-opening polymerization.So owing to be that mass polymerization functionalization epoxy compounds and functionalization acid anhydrides can dissolve each other, reaction product is purer.
According to R of the present invention
1, R
2Be the functionalization group, and both are inequality, and the functionalization group is the functionalization group in functionalization epoxy compounds and the functionalization acid anhydrides, and R
1With R
2Mol ratio be 1: 1.The functionalization epoxy compounds that the present invention uses is preferably: 2-((2-methoxy ethoxy) methyl) oxyethane, 2-((2 (2-(2-methoxy ethoxy)) oxyethyl group) methyl) oxyethane, 2-2,5,8,11-four oxygen dodecyl oxyethane, 3-epoxy ethyl methoxypropionic acid, N, N-dimethyl-3-epoxy ethyl methoxyethyl amine or N, N-diethyl-3-epoxy ethyl methoxyethyl amine.Functionalization acid anhydrides that the present invention uses is preferably and is Succinic anhydried, Pyroglutaric acid, 3-t-butoxycarbonyl amino Pyroglutaric acid, 3-N, N-dimethylamino Pyroglutaric acid or 3-N, N-diethylamino Pyroglutaric acid.Can make a series of polyester product by different initiators with different proportioning raw materials like this with functionalization group.
Functionalized polyester provided by the invention includes but not limited to following material: poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid), poly-(2-((2-(2-methoxy ethoxy) oxyethyl group) methyl) oxyethane-co-Pyroglutaric acid), poly-(2-2,5,8,11-four oxygen dodecyl oxyethane-co-Pyroglutaric acids), poly-(3-epoxy ethyl methoxypropionic acid-co-Pyroglutaric acid), poly-(N, N-dimethyl-3-epoxy ethyl methoxyethyl amine-co-Pyroglutaric acid), poly-(N, N-diethyl-3-epoxy ethyl methoxyethyl amine-co-Pyroglutaric acid), poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Succinic anhydried), poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-3-t-butoxycarbonyl amino Pyroglutaric acid), poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-3-N, N-dimethylamino Pyroglutaric acid), poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-3-N, N-diethylamino Pyroglutaric acid), poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid)-ethylene glycol-poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid), poly glycol monomethyl ether-b-gathers (2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid), poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid)-b-polyoxyethylene glycol-b-poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid).Above-mentioned functions polyester number-average molecular weight is 3000～120000; Dispersity is 1.10～1.30.
The present invention also provides a kind of method for preparing functionalized polyester, comprising: a) under anhydrous condition, be that 1: 1 functionalization epoxy compounds mixes with the functionalization acid anhydrides with aluminum isopropylate and mol ratio, obtain mixture;
B) heat described mixture 34h～38h down at 100 ℃～150 ℃, make described mixture polymerization reaction take place, obtain polymkeric substance;
C) with getting filtrate after described polymkeric substance dilution, the filtration, more described filtrate is carried out sedimentation, washing, drying operation and finally obtain functionalized polyester.
According to the present invention, at first under anhydrous condition, aluminum isopropylate is mixed with the epoxy compounds and the functionalization acid anhydrides of functionalization, the mol ratio of the epoxy compounds of functionalization and described functionalization acid anhydrides is 1: 1, described functionalization epoxy compounds is: 2-((2-methoxy ethoxy) methyl) oxyethane, 2-((2 (2-(2-methoxy ethoxy)) oxyethyl group) methyl) oxyethane, 2-2,5,8,11-four oxygen dodecyl oxyethane, 3-epoxy ethyl methoxypropionic acid, N, N-dimethyl-3-epoxy ethyl methoxyethyl amine or N, N-diethyl-3-epoxy ethyl methoxyethyl amine, described functionalization acid anhydrides is a Succinic anhydried, Pyroglutaric acid, 3-t-butoxycarbonyl amino Pyroglutaric acid, 3-N, N-dimethylamino Pyroglutaric acid or 3-N, N-diethylamino Pyroglutaric acid.The present invention preferably uses above-mentioned substance to carry out different reactions, and the performance between the test products therefrom.
According to the present invention, the mol ratio of the epoxy compounds of aluminum isopropylate and functionalization and functionalization acid anhydrides is 1: 15～750: 15～750.With above-mentioned 3 kinds of compound, obtain mixture.Wherein aluminum isopropylate be initiator be again catalyzer, can cause the epoxy compounds of functionalization and the acid anhydrides of functionalization and carry out polymerization, obtain functionalized polyester.Stir described mixture and intensification gradually, maintain the temperature at 100 ℃～150 ℃, be preferably 110 ℃～140 ℃, mixture is thickness more and more, and the control stir speed (S.S.) keeps polyreaction to carry out in a stable viscosity.Heat beginning according to the present invention and stop heating behind 34h～38h, obtain polymkeric substance, add the trichloromethane diluted polymer when stirring in reaction system, the viscosity of polymkeric substance descends gradually, mobile increasing.Filter the chloroform soln of described polymer poly compound then, remove insoluble impurity wherein, obtaining filtrate, to join volume ratio again be in 1: 6～10: 1 the mixing solutions of ether, normal hexane and ethyl acetate, polymkeric substance is separated out from trichloromethane, the throw out that the group of formation is cotton-shaped takes out described throw out, re-uses normal hexane washing precipitate surface, dry 20h～26h under 20 ℃～30 ℃ obtains functionalized polyester.
The present invention also provides a kind of preparation method of functionalized polyester, comprise: under anhydrous condition, it is that 1: 1 functionalization epoxy compounds and functionalization acid anhydrides mixes that small molecular alcohol or fusing point are lower than 120 ℃ polymeric initiator, stannous iso caprylate, mol ratio, obtains mixture;
Under 100 ℃～150 ℃, heat and stir described mixture 34h～38h, make described mixture polymerization reaction take place, obtain polymkeric substance;
With getting filtrate after described polymkeric substance dilution, the filtration, more described filtrate is carried out sedimentation, washing, drying operation and finally obtain functionalized polyester.
According to the present invention, at first under anhydrous condition, small molecular alcohol or fusing point are lower than 120 ℃ polymeric initiator, stannous iso caprylate, mol ratio is that 1: 1 functionalization epoxy compounds and functionalization acid anhydrides mixes, described small molecular alcohol includes but not limited to phenylcarbinol, Virahol or ethylene glycol, described fusing point is lower than 120 ℃ polymeric initiator and includes but not limited to polyoxyethylene glycol or poly glycol monomethyl ether, described functionalization epoxy compounds is: 2-((2-methoxy ethoxy) methyl) oxyethane, 2-((2 (2-(2-methoxy ethoxy)) oxyethyl group) methyl) oxyethane, 2-2,5,8,11-four oxygen dodecyl oxyethane, 3-epoxy ethyl methoxypropionic acid, N, N-dimethyl-3-epoxy ethyl methoxyethyl amine or N, N-diethyl-3-epoxy ethyl methoxyethyl amine, described functionalization acid anhydrides is a Succinic anhydried, Pyroglutaric acid, 3-t-butoxycarbonyl amino Pyroglutaric acid, 3-N, N-dimethylamino Pyroglutaric acid or 3-N, N-diethylamino Pyroglutaric acid.The present invention preferably uses above-mentioned substance to carry out different reactions, and the performance between the test products therefrom.Described small molecular alcohol or fusing point are lower than 120 ℃ polymeric initiator and the mol ratio of described stannous iso caprylate and described functionalization epoxy compounds and functionalization acid anhydrides is 1: 2000～100000: 5～250: 5～250.Wherein, small molecular alcohol and fusing point are lower than 120 ℃ polymeric initiator as initiator, and stannous iso caprylate is a catalyzer, and functionalization epoxy compounds and functionalization acid anhydrides are reactant.Initiator initiation reaction thing polymerization reaction take place obtains reaction product, and catalyzer can generate the speed of free radical by the catalysis initiator, thereby improves reaction efficiency.
With initiator, after catalyzer and reactant mix, stir described mixture and intensification gradually, maintain the temperature at 100 ℃～150 ℃, be preferably 110 ℃～140 ℃, mixture is thickness more and more, the control stir speed (S.S.) keeps polyreaction to carry out in a stable viscosity.Heat beginning according to the present invention and stop heating behind 34h～38h, obtain polymkeric substance, add the trichloromethane diluted polymer when stirring in reaction system, the viscosity of polymkeric substance descends gradually, mobile increasing.Filter the chloroform soln of described polymkeric substance then, remove insoluble impurity wherein, obtaining filtrate, to join volume ratio again be in 1: 6～10: 1 the mixing solutions of ether, normal hexane and ethyl acetate, polymkeric substance is separated out from trichloromethane, the throw out that the group of formation is cotton-shaped takes out described throw out, re-uses normal hexane washing precipitate surface, dry 20h～26h under 20 ℃～30 ℃ obtains functionalized polyester.
Above-mentioned two kinds of methods can prepare functionalized polyester provided by the invention, first method be by aluminum isopropylate as initiator and catalyzer, cause catalytic polymerization, an end of gained polyester molecule has a sec.-propyl; And second method use small molecular alcohol or fusing point are lower than 120 ℃ polymer as initiator, stannous iso caprylate is as catalyzer, one end of the polyester molecule that reaction obtains after finishing is connected with a phenmethyl, sec.-propyl, poly glycol monomethyl ether, or 2 polyester molecules link to each other by ethylene glycol or polyoxyethylene glycol, so the difference of method can be prepared different functionalized polyesters, but bright the having of providing of this law is provided the product of two kinds of method preparations
The functionalized polyester of structure.
For more detailed elaboration the present invention, below be specific embodiment, but only be most preferred embodiment of the present invention.
Embodiment 1: the preparation of poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid) of different chain length degree
Under anhydrous condition, take by weighing 7 parts of quality and be 2-((2-methoxy ethoxy) methyl) oxyethane of 5.0g and the Pyroglutaric acid of 4.32g, put into 7 exsiccant reaction flasks, add 0.258g respectively, 0.052g, 0.026g, 0.013g, 0.009g, 0.006g, 0.005g aluminum isopropylate, under 120 ℃ of bulk conditions and stirrer stirring, react 36h, reaction finishes back trichloromethane diluting reaction system, and the elimination insolubles is at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, ether wherein, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, use the normal hexane washed product, 25 ℃ of following vacuum-drying 24h obtain in poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid) of different chain length degree.The gained functionalized polyester sees Table one.
Poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid) of table one different chain length degree
| Experiment is compiled | ??I/N 1/N 2 | ??Mn(g.mol -1) | ??DP 1 | ??DP 2 | Reaction yield (%) |
| ??1 | ??1∶30∶30 | ??2770 | ??10 | ??11 | ??86.1 |
| ??2 | ??1∶150∶150 | ??12110 | ??50 | ??49 | ??87.7 |
| ??3 | ??1∶300∶300 | ??25150 | ??100 | ??102 | ??86.3 |
| ??4 | ??1∶600∶600 | ??50000 | ??200 | ??203 | ??85.1 |
| ??5 | ??1∶900∶900 | ??73370 | ??300 | ??298 | ??89.3 |
| ??6 | ??1∶1200∶1200 | ??95750 | ??400 | ??389 | ??82.9 |
| ??7 | ??1∶1500∶1500 | ??124040 | ??500 | ??504 | ??89.7 |
In the last table, I/N
1/ N
2The mol ratio of aluminum isopropylate, 2-((2-methoxy ethoxy) methyl) oxyethane and Pyroglutaric acid when feeding intake; Mn is the number-average molecular weight of poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid), by
1H NMR measures and obtains; DP1 is the theoretical mean polymerisation degree of poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid); DP1 is the mean polymerisation degree of poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid), by
1H NMR measures and obtains; Reaction yield is the ratio of quality with the quality of theoretical poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid) that obtains of actual poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid) that obtains.
Embodiment 2: the preparation of poly-(2-((2-(2-methoxy ethoxy) oxyethyl group) methyl) oxyethane-co-Pyroglutaric acid):
Under anhydrous condition, take by weighing the Pyroglutaric acid of the 2-that quality is 6.67g ((2-(2-methoxy ethoxy) oxyethyl group) methyl) oxyethane and 4.32g, put into the exsiccant reaction flask, add the 0.026g aluminum isopropylate, under 120 ℃ of bulk conditions and stirrer stirring, react 36h, reaction finishes back trichloromethane diluting reaction system, the elimination insolubles, at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, ether wherein, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, use the normal hexane washed product, 25 ℃ of following vacuum-drying 24h are gathered (2-((2-(2-methoxy ethoxy) oxyethyl group) methyl) oxyethane-co-Pyroglutaric acid).By
1It is 100 that H NMR measures product degree of polymerization, and number-average molecular weight is 29060.Reaction yield is: 86.1%.
Embodiment 3: the preparation of poly-(2-2,5,8,11-four oxygen dodecyl oxyethane-co-Pyroglutaric acids):
Under anhydrous condition, take by weighing the 2-2 that quality is 8.33g, 5,8, the Pyroglutaric acid of 11-four oxygen dodecyl oxyethane and 4.32g is put into the exsiccant reaction flask, add the 0.026g aluminum isopropylate, react 36h under 120 ℃ of bulk conditions and stirrer stirring, reaction finishes back trichloromethane diluting reaction system, elimination insolubles, at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, ether wherein, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, uses the normal hexane washed product, 25 ℃ of following vacuum-drying 24h, gathered (2-2,5,8,11-four oxygen dodecyl oxyethane-co-Pyroglutaric acids).By
1It is 99 that H NMR measures product degree of polymerization, and number-average molecular weight is 33130.Reaction yield is: 88.9%.
Embodiment 4: the preparation of poly-(3-epoxy ethyl methoxypropionic acid-co-Pyroglutaric acid):
Under anhydrous condition, taking by weighing quality is the 3-epoxy ethyl methoxypropionic acid of 5.0g and the Pyroglutaric acid of 4.32g, put into the exsiccant reaction flask, add the 0.026g aluminum isopropylate, under 120 ℃ of bulk conditions and stirrer stirring, react 36h, reaction finishes back trichloromethane diluting reaction system, the elimination insolubles, at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, ether wherein, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, use the normal hexane washed product, 25 ℃ of following vacuum-drying 24h are gathered (3-epoxy ethyl methoxypropionic acid-co-Pyroglutaric acid).By
1It is 98 that H NMR measures product degree of polymerization, and number-average molecular weight is 24170.Reaction yield is: 89.5%.
Embodiment 5: the preparation of poly-(N, N-dimethyl-3-epoxy ethyl methoxyethyl amine-co-Pyroglutaric acid):
Under anhydrous condition, take by weighing the N that quality is 5.50g, the Pyroglutaric acid of N-dimethyl-3-epoxy ethyl methoxyethyl amine and 4.32g, put into the exsiccant reaction flask, add the 0.026g aluminum isopropylate, under 120 ℃ of bulk conditions and stirrer stirring, react 36h, reaction finishes back trichloromethane diluting reaction system, the elimination insolubles is at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, wherein ether, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, use the normal hexane washed product, 25 ℃ of following vacuum-drying 24h are gathered (N, N-dimethyl-3-epoxy ethyl methoxyethyl amine-co-Pyroglutaric acid).By
1It is 102 that H NMR measures product degree of polymerization, and number-average molecular weight is 26480.Reaction yield is: 87.3%.
Embodiment 6: the preparation of poly-(N, N-diethyl-3-epoxy ethyl methoxyethyl amine-co-Pyroglutaric acid):
Under anhydrous condition, take by weighing the N that quality is 6.55g, the Pyroglutaric acid of N-diethyl-3-epoxy ethyl methoxyethyl amine and 4.32g, put into the exsiccant reaction flask, add the 0.026g aluminum isopropylate, under 120 ℃ of bulk conditions and stirrer stirring, react 36h, reaction finishes back trichloromethane diluting reaction system, the elimination insolubles is at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, wherein ether, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, use the normal hexane washed product, 25 ℃ of following vacuum-drying 24h are gathered (N, N-diethyl-3-epoxy ethyl methoxyethyl amine-co-Pyroglutaric acid).By
1It is 97 that H NMR measures product degree of polymerization, and number-average molecular weight is 27930.Reaction yield is: 88.9%.
Embodiment 7: the preparation of poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Succinic anhydried):
Under anhydrous condition, take by weighing the Succinic anhydried of the 2-that quality is 5.0g ((2-methoxy ethoxy) methyl) oxyethane and 3.79g, put into the exsiccant reaction flask, add the 0.026g aluminum isopropylate, under 120 ℃ of bulk conditions and stirrer stirring, react 36h, reaction finishes back trichloromethane diluting reaction system, the elimination insolubles, at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, ether wherein, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, use the normal hexane washed product, 25 ℃ of following vacuum-drying 24h are gathered (2-((2-methoxy ethoxy) methyl) oxyethane-co-Succinic anhydried).By
1It is 98 that H NMR measures product degree of polymerization, and number-average molecular weight is 22820.Reaction yield is: 88.9%.
Embodiment 8: the preparation of poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-3-t-butoxycarbonyl amino Pyroglutaric acid)
Under anhydrous condition, take by weighing the 3-t-butoxycarbonyl amino Pyroglutaric acid of the 2-that quality is 5.0g ((2-methoxy ethoxy) methyl) oxyethane and 8.68g, put into the exsiccant reaction flask, add the 0.026g aluminum isopropylate, under 120 ℃ of bulk conditions and stirrer stirring, react 36h, reaction finishes back trichloromethane diluting reaction system, the elimination insolubles, at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, ether wherein, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, use the normal hexane washed product, 25 ℃ of following vacuum-drying 24h are gathered (2-((2-methoxy ethoxy) methyl) oxyethane-co-3-t-butoxycarbonyl amino Pyroglutaric acid).By
1It is 99 that HNMR measures product degree of polymerization, and number-average molecular weight is 35798.Reaction yield is: 89.5%.
Embodiment 9: the preparation of poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-3-N, N-dimethylamino Pyroglutaric acid):
Under anhydrous condition, take by weighing the 3-N of the 2-that quality is 5.0g ((2-methoxy ethoxy) methyl) oxyethane and 5.95g, N-dimethylamino Pyroglutaric acid, put into the exsiccant reaction flask, add the 0.026g aluminum isopropylate, under 120 ℃ of bulk conditions and stirrer stirring, react 36h, reaction finishes back trichloromethane diluting reaction system, the elimination insolubles, at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, ether wherein, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, use the normal hexane washed product, 25 ℃ of following vacuum-drying 24h are gathered (2-((2-methoxy ethoxy) methyl) oxyethane-co-3-N, N-dimethylamino Pyroglutaric acid).By
1It is 96 that HNMR measures product degree of polymerization, and number-average molecular weight is 27930.Reaction yield is: 86.7%.
Embodiment 10: the preparation of poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-3-N, N-diethylamino Pyroglutaric acid):
Under anhydrous condition, take by weighing the 3-N of the 2-that quality is 5.0g ((2-methoxy ethoxy) methyl) oxyethane and 7.01g, N-diethylamino Pyroglutaric acid, put into the exsiccant reaction flask, add the 0.026g aluminum isopropylate, under 120 ℃ of bulk conditions and stirrer stirring, react 36h, reaction finishes back trichloromethane diluting reaction system, the elimination insolubles, at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, ether wherein, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, use the normal hexane washed product, 25 ℃ of following vacuum-drying 24h are gathered (2-((2-methoxy ethoxy) methyl) oxyethane-co-3-N, N-diethylamino Pyroglutaric acid).By
1It is 99 that HNMR measures product degree of polymerization, and number-average molecular weight is 31440.Reaction yield is: 85.6%.
Embodiment 11: the preparation of poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid) of different chain length degree:
Under anhydrous condition, take by weighing 7 parts of quality and be 2-((2-methoxy ethoxy) methyl) oxyethane of 5.0g and the Pyroglutaric acid of 4.32g, put into 7 exsiccant reaction flasks, add 0.409g respectively, 0.082g, 0.041g, 0.020g, 0.014g, 0.010g, 0.008g phenylcarbinol and 0.077g stannous iso caprylate, under 120 ℃ of bulk conditions and stirrer stirring, react 36h, reaction finishes back trichloromethane diluting reaction system, and the elimination insolubles is at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, ether wherein, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, use the normal hexane washed product, 25 ℃ of following vacuum-drying 24h obtain in poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid) of different chain length degree.The gained functionalized polyester sees Table two.
Poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid) of table two different chain length degree
| Experiment is compiled | ??I/N 1/N 2 | ??Mn(g.mol -1) | ??DP 1 | ??DP 2 | Reaction yield (%) |
| ??1 | ??1∶10∶10 | ??2320 | ??10 | ??9 | ??89.6 |
| ??2 | ??1∶50∶50 | ??11670 | ??50 | ??47 | ??87.9 |
| ??3 | ??1∶100∶100 | ??23720 | ??100 | ??96 | ??89.4 |
| ??4 | ??1∶200∶200 | ??49550 | ??200 | ??201 | ??88.8 |
| ??5 | ??1∶300∶300 | ??73170 | ??300 | ??297 | ??86.9 |
| ??6 | ??1∶400∶400 | ??99000 | ??400 | ??402 | ??87.5 |
| ??7 | ??1∶500∶500 | ??123840 | ??500 | ??503 | ??86.3 |
In the last table, I/N
1/ N
2The mol ratio of phenylcarbinol, 2-((2-methoxy ethoxy) methyl) oxyethane and Pyroglutaric acid when feeding intake; Mn is the number-average molecular weight of poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid), by
1H NMR measures and obtains; DP
1Theoretical mean polymerisation degree for poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid); DP
2Be the mean polymerisation degree of poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid), by
1H NMR measures and obtains; Reaction yield is the ratio of quality with the quality of theoretical poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid) that obtains of actual poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid) that obtains.
Embodiment 12: the preparation of poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid)-ethylene glycol-poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid)
Under anhydrous condition, take by weighing the Pyroglutaric acid of the 2-that quality is 5.0g ((2-methoxy ethoxy) methyl) oxyethane and 4.32g, put into the exsiccant reaction flask, add 0.012g ethylene glycol and 0.077g stannous iso caprylate, under 120 ℃ of bulk conditions and stirrer stirring, react 36h, reaction finishes back trichloromethane diluting reaction system, the elimination insolubles, at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, ether wherein, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, use the normal hexane washed product, 25 ℃ of following vacuum-drying 24h are gathered (2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid)-ethylene glycol-poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid).By
1It is 100 that H NMR measures product degree of polymerization, and number-average molecular weight is 24660.Reaction yield is: 89.3%.
Embodiment 13: the preparation of the poly glycol monomethyl ether-b-of different chain length degree poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid):
Under anhydrous condition, take by weighing 4 parts of quality and be 2-((2-methoxy ethoxy) methyl) oxyethane of 5.0g and the Pyroglutaric acid of 4.34g, put into 4 exsiccant reaction flasks, add 0.076g respectively, 0.757g, 0.892g, 3.783g poly glycol monomethyl ether and 0.077g stannous iso caprylate, under 120 ℃ of bulk conditions and stirrer stirring, react 36h, reaction finishes back trichloromethane diluting reaction system, the elimination insolubles, at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, wherein ether, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, uses the normal hexane washed product, 25 ℃ of following vacuum-drying 2h, the poly glycol monomethyl ether-b-that obtains the different chain length degree gathers (2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid).The gained functionalized polyester sees Table three.
Poly glycol monomethyl ether-the b-of table three different chain length degree gathers (2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid)
| Experiment numbers | ??I/N 1/N 2 | ??Mn 1(g.mol -1) | ??Mn 2(g.mol -1) | ??DP | Reaction yield (%) |
| ??1 | ??1∶100∶100 | ??200 | ??23570 | ??95 | ??86.4 |
| ??2 | ??1∶100∶100 | ??2000 | ??26100 | ??98 | ??89.7 |
| ??3 | ??1∶100∶100 | ??5000 | ??28860 | ??97 | ??85.6 |
| ??4 | ??1∶100∶100 | ??10000 | ??33620 | ??96 | ??87.9 |
In the last table, I/N
1/ N
2The mol ratio of poly glycol monomethyl ether, 2-((2-methoxy ethoxy) methyl) oxyethane and Pyroglutaric acid when feeding intake; Mn
1Be molecular weight as the poly glycol monomethyl ether of initiator; Mn
2Be the number-average molecular weight of poly glycol monomethyl ether-b-poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid), by
1H NMR measures and obtains; DP is the mean polymerisation degree that gathers (2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid) that poly glycol monomethyl ether causes, by
1H NMR measures and obtains; Reaction yield is the ratio of quality with the quality of the theoretical poly glycol monomethyl ether-b-that obtains poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid) of the actual poly glycol monomethyl ether-b-that obtains poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid).
Embodiment 14: the preparation of poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-the Pyroglutaric acid)-b-polyoxyethylene glycol-b-poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid) of different chain length degree:
Under anhydrous condition, take by weighing 4 parts of quality and be 2-((2-methoxy ethoxy) methyl) oxyethane of 5.0g and the Pyroglutaric acid of 4.32g, put into 4 exsiccant reaction flasks, add 0.076g respectively, 0.757g, 0.892g, 3.783g polyoxyethylene glycol and 0.077g stannous iso caprylate, under 120 ℃ of bulk conditions and stirrer stirring, react 36h, reaction finishes back trichloromethane diluting reaction system, the elimination insolubles, at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, ether wherein, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, use the normal hexane washed product, 25 ℃ of following vacuum-drying 24h, poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-the Pyroglutaric acid)-b-polyoxyethylene glycol-b-that obtains the different chain length degree gathers (2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid).The gained functionalized polyester sees Table four.
Poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-the Pyroglutaric acid)-b-polyoxyethylene glycol-b-poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid) of table four different chain length degree
| Experiment numbers | ??I/N 1/N 2 | ??Mn 1(g.mol -1) | ??Mn 2(g.mol -1) | ??DP | Reaction yield (%) |
| ??1 | ??1∶100∶100 | ??200 | ??24550 | ??99 | ??87.5 |
| ??2 | ??1∶100∶100 | ??2000 | ??25860 | ??97 | ??89.5 |
| ??3 | ??1∶100∶100 | ??5000 | ??29600 | ??100 | ??86.7 |
| ??4 | ??1∶100∶100 | ??10000 | ??34110 | ??98 | ??87.8 |
In the last table, I/N
1/ N
2The mol ratio of polyoxyethylene glycol, 2-((2-methoxy ethoxy) methyl) oxyethane and Pyroglutaric acid when feeding intake; Mn
1Be molecular weight as the polyoxyethylene glycol of initiator; Mn
2Be the number-average molecular weight of poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid)-b-polyoxyethylene glycol-b-poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid), by
1H NMR measures and obtains; DP is the mean polymerisation degree that gathers (2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid) that polyoxyethylene glycol causes, by
1H NMR measures and obtains; Reaction yield is the ratio of quality with the quality of theoretical poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-the Pyroglutaric acid)-b-polyoxyethylene glycol-b-poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid) that obtains of actual poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-the Pyroglutaric acid)-b-polyoxyethylene glycol-b-poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Pyroglutaric acid) that obtains.
Embodiment 15: the preparation of poly-(2-((2-(2-methoxy ethoxy) oxyethyl group) methyl) oxyethane-co-Pyroglutaric acid):
Under anhydrous condition, take by weighing the Pyroglutaric acid of the 2-that quality is 6.67g ((2-(2-methoxy ethoxy) oxyethyl group) methyl) oxyethane and 4.32g, put into the exsiccant reaction flask, add 0.041g phenylcarbinol and 0.077g stannous iso caprylate, under 120 ℃ of bulk conditions and stirrer stirring, react 36h, reaction finishes back trichloromethane diluting reaction system, the elimination insolubles, at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, ether wherein, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, use the normal hexane washed product, 25 ℃ of following vacuum-drying 24h are gathered (2-((2-(2-methoxy ethoxy) oxyethyl group) methyl) oxyethane-co-Pyroglutaric acid).By
1It is 98 that H NMR measures product degree of polymerization, and number-average molecular weight is 28530.Reaction yield is: 88.9%.
Embodiment 16: the preparation of poly-(2-2,5,8,11-four oxygen dodecyl oxyethane-co-Pyroglutaric acids):
Under anhydrous condition, take by weighing the 2-2 that quality is 8.33g, 5,8, the Pyroglutaric acid of 11-four oxygen dodecyl oxyethane and 4.32g is put into the exsiccant reaction flask, add 0.041g phenylcarbinol and 0.077g stannous iso caprylate, react 36h under 120 ℃ of bulk conditions and stirrer stirring, reaction finishes back trichloromethane diluting reaction system, elimination insolubles, at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, ether wherein, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, uses the normal hexane washed product, 25 ℃ of following vacuum-drying 24h, gathered (2-2,5,8,11-four oxygen dodecyl oxyethane-co-Pyroglutaric acids).By
1It is 101 that H NMR measures product degree of polymerization, and number-average molecular weight is 33840.Reaction yield is: 86.3%.
Embodiment 17: the preparation of poly-(3-epoxy ethyl methoxypropionic acid-co-Pyroglutaric acid)
Under anhydrous condition, taking by weighing quality is the 3-epoxy ethyl methoxypropionic acid of 5.0g and the Pyroglutaric acid of 4.32g, put into the exsiccant reaction flask, add 0.041g phenylcarbinol and 0.077g stannous iso caprylate, under 120 ℃ of bulk conditions and stirrer stirring, react 36h, reaction finishes back trichloromethane diluting reaction system, the elimination insolubles, at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, ether wherein, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, use the normal hexane washed product, 25 ℃ of following vacuum-drying 24h are gathered (3-epoxy ethyl methoxypropionic acid-co-Pyroglutaric acid).By
1It is 98 that H NMR measures product degree of polymerization, and number-average molecular weight is 24950.Reaction yield is: 87.9%.
Embodiment 18: the preparation of poly-(N, N-dimethyl-3-epoxy ethyl methoxyethyl amine-co-Pyroglutaric acid):
Under anhydrous condition, take by weighing the N that quality is 5.49g, the Pyroglutaric acid of N-dimethyl-3-epoxy ethyl methoxyethyl amine and 4.32g, put into the exsiccant reaction flask, add 0.041g phenylcarbinol and 0.077g stannous iso caprylate, under 120 ℃ of bulk conditions and stirrer stirring, react 3h, reaction finishes back trichloromethane diluting reaction system, the elimination insolubles is at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, wherein ether, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, use the normal hexane washed product, 25 ℃ of following vacuum-drying 24h are gathered (N, N-dimethyl-3-epoxy ethyl methoxyethyl amine-co-Pyroglutaric acid).By
1It is 96 that H NMR measures product degree of polymerization, and number-average molecular weight is 24970.Reaction yield is: 86.7%.
Embodiment 19: the preparation of poly-(N, N-diethyl-3-epoxy ethyl methoxyethyl amine-co-Pyroglutaric acid):
Under anhydrous condition, take by weighing the N that quality is 5.49g, the Pyroglutaric acid of N-diethyl-3-epoxy ethyl methoxyethyl amine and 6.55g, put into the exsiccant reaction flask, add 0.04g phenylcarbinol and 0.077g stannous iso caprylate, under 120 ℃ of bulk conditions and stirrer stirring, react 36h, reaction finishes back trichloromethane diluting reaction system, the elimination insolubles is at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, wherein ether, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, use the normal hexane washed product, 25 ℃ of following vacuum-drying 24h are gathered (N, N-diethyl-3-epoxy ethyl methoxyethyl amine-co-Pyroglutaric acid).By
1It is 98 that H NMR measures product degree of polymerization, and number-average molecular weight is 28230.Reaction yield is: 87.9%.
Embodiment 20: the preparation of poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Succinic anhydried):
Under anhydrous condition, take by weighing the Succinic anhydried of the 2-that quality is 5.0g ((2-methoxy ethoxy) methyl) oxyethane and 3.79g, put into the exsiccant reaction flask, add 0.041g phenylcarbinol and 0.077g stannous iso caprylate respectively, under 120 ℃ of bulk conditions and stirrer stirring, react 36h, reaction finishes back trichloromethane diluting reaction system, the elimination insolubles, at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, ether wherein, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, use the normal hexane washed product, 25 ℃ of following vacuum-drying 24h obtain in poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-Succinic anhydried) of different chain length degree.By
1It is 103 that HNMR measures product degree of polymerization, and number-average molecular weight is 24000.Reaction yield is: 86.9%.
Embodiment 20: the preparation of poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-3-t-butoxycarbonyl amino Pyroglutaric acid):
Under anhydrous condition, take by weighing the 3-t-butoxycarbonyl amino Pyroglutaric acid of the 2-that quality is 5.0g ((2-methoxy ethoxy) methyl) oxyethane and 8.68g, put into the exsiccant reaction flask, add 0.041g phenylcarbinol and 0.077g stannous iso caprylate respectively, under 120 ℃ of bulk conditions and stirrer stirring, react 36h, reaction finishes back trichloromethane diluting reaction system, the elimination insolubles, at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, ether wherein, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, use the normal hexane washed product, 25 ℃ of following vacuum-drying 24h obtain in poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-3-t-butoxycarbonyl amino Pyroglutaric acid) of different chain length degree.By
1It is 96 that H NMR measures product degree of polymerization, and number-average molecular weight is 34760.Reaction yield is: 89.6%.
Embodiment 21: the preparation of poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-3-N, N-dimethylamino Pyroglutaric acid):
Under anhydrous condition, take by weighing the 3-N of the 2-that quality is 5.0g ((2-methoxy ethoxy) methyl) oxyethane and 5.95g, N-dimethylamino Pyroglutaric acid, put into the exsiccant reaction flask, add 0.041g phenylcarbinol and 0.077g stannous iso caprylate respectively, under 120 ℃ of bulk conditions and stirrer stirring, react 36h, reaction finishes back trichloromethane diluting reaction system, the elimination insolubles, at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, ether wherein, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, use the normal hexane washed product, 25 ℃ of following vacuum-drying 24h obtain poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-3-N, the N-dimethylamino Pyroglutaric acid) of different chain length degree.By
1It is 97 that H NMR measures product degree of polymerization, and number-average molecular weight is 28140.Reaction yield is: 85.4%.
Embodiment 22: the preparation of poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-3-N, N-diethylamino Pyroglutaric acid):
Under anhydrous condition, take by weighing the 3-N of the 2-that quality is 5.0g ((2-methoxy ethoxy) methyl) oxyethane and 7.01g, N-diethylamino Pyroglutaric acid, put into the exsiccant reaction flask, add 0.041g phenylcarbinol and 0.077g stannous iso caprylate respectively, under 120 ℃ of bulk conditions and stirrer stirring, react 36h, reaction finishes back trichloromethane diluting reaction system, the elimination insolubles, at ether, sedimentation in the mixed solvent of normal hexane and ethyl acetate, ether wherein, the volume ratio of normal hexane and ethyl acetate is 1: 8: 1, use the normal hexane washed product, 25 ℃ of following vacuum-drying 24h obtain poly-(2-((2-methoxy ethoxy) methyl) oxyethane-co-3-N, the N-diethylamino Pyroglutaric acid) of different chain length degree.By
1It is 101 that H NMR measures product degree of polymerization, and number-average molecular weight is 32130.Reaction yield is: 89.8%.
The invention provides a kind of functionalized polyester, be to carry out polymerization and a kind of polyester of obtaining by functionalization epoxy compounds and functionalization acid anhydrides, because the existence such as 2-(2-methoxy ethoxy) methyl of the functional group on the functionalization epoxy compounds, 2-(2 (2-(2-methoxy ethoxy)) oxyethyl group) methyl, 2-2,5,8, groups such as 11-four oxygen dodecyls all have very strong temperature, the pH value, ionic strength sensibility, and the functional group figure that has on the functionalization acid anhydrides has the pH value, the susceptibility that ionic strength changes, also just had multiple response so have the epoxy compounds of described functionalization group and polyester that the acid anhydrides polymerization obtains, and the structural unit good biocompatibility that is contained in the polyester, and because the existence of ester bond makes polyester biodegradable.So functionalized polyester provided by the invention had both had multiple response, had biocompatibility and biodegradable again.The present invention also provides a kind of preparation method of functionalized polyester, and this method is simple to operate, and being swift in response can be good at realizing the control of polyester manufacture process.
More than a kind of functionalized polyester provided by the invention and preparation method thereof is described in detail; having used specific case herein sets forth principle of the present invention and embodiment; the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; should be understood that; for those skilled in the art; under the prerequisite that does not break away from the principle of the invention; can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. a functionalized polyester is characterized in that, general structure is:
Wherein R is that the fusing point of residue after isopropoxy, the small molecular alcohol dehydrogenation or dehydrogenation is lower than the residue that 120 ℃ polymeric initiator forms;
R
1, R
2For functionalization group inequality, described functionalization group are functionalization group in functionalization epoxy compounds and functionalization pentabasic acid acid anhydride or the hexa-atomic acid anhydrides; Described R
1With R
2Mol ratio be 1: 1;
M=1 or 2;
The number-average molecular weight of described functionalized polyester is 3000～120000; Dispersity is 1.10～1.30.
2. functionalized polyester according to claim 1, it is characterized in that, described functionalization epoxy compounds is: 2-((2-methoxy ethoxy) methyl) oxyethane, 2-((2 (2-(2-methoxy ethoxy)) oxyethyl group) methyl) oxyethane, 2-2,5,8,11-four oxygen dodecyl oxyethane, 3-epoxy ethyl methoxypropionic acid, N, N-dimethyl-3-epoxy ethyl methoxyethyl amine or N, N-diethyl-3-epoxy ethyl methoxyethyl amine.
3. functionalized polyester according to claim 1 is characterized in that, described functionalization acid anhydrides is: Succinic anhydried, Pyroglutaric acid, 3-t-butoxycarbonyl amino Pyroglutaric acid, 3-N, N-dimethylamino Pyroglutaric acid or 3-N, N-diethylamino Pyroglutaric acid.
4. functionalized polyester according to claim 1 is characterized in that, described small molecular alcohol is: methyl alcohol, Virahol or ethylene glycol.
5. functionalized polyester according to claim 1 is characterized in that, fusing point is lower than 120 ℃ polymeric initiator and is: number-average molecular weight is 200～10000 polyoxyethylene glycol or poly glycol monomethyl ether.
6. the preparation method of a functionalized polyester is characterized in that, comprising:
A) under anhydrous condition, be that 1: 1 functionalization epoxy compounds mixes with the functionalization acid anhydrides with aluminum isopropylate and mol ratio, obtain mixture;
B) under 100 ℃～150 ℃, heat and stir described mixture 34h～38h, make described mixture polymerization reaction take place, obtain polymkeric substance;
C) with getting filtrate after described polymkeric substance dilution, the filtration, more described filtrate is carried out sedimentation, washing, drying operation and finally obtain functionalized polyester.
7. preparation method according to claim 6 is characterized in that step c specifically comprises: c1), use trichloromethane to dilute the polymkeric substance that described step b) obtains, and filter, remove insolubles, obtain filtrate;
C2), with c2) filtrate that obtains is sedimentation in 1: 6～10: 1 the mixing solutions of ether, normal hexane and ethyl acetate in volume ratio, obtains throw out;
C3), wash described throw out, and, obtain functionalized polyester at 20 ℃～30 ℃ dry 20h～26h down with normal hexane.
8. preparation method according to claim 7 is characterized in that, the mol ratio of described aluminum isopropylate and described functionalization epoxy compounds and functionalization acid anhydrides is 1: 15～750: 15～750.
9. the preparation method of a functionalized polyester is characterized in that, comprising:
Under anhydrous condition, it is that 1: 1 functionalization epoxy compounds and functionalization acid anhydrides mixes that small molecular alcohol or fusing point are lower than 120 ℃ polymeric initiator, stannous iso caprylate, mol ratio, obtains mixture;
Under 100 ℃～150 ℃, heat and stir described mixture 34h～38h, make described mixture polymerization reaction take place, obtain polymkeric substance;
With getting filtrate after described polymkeric substance dilution, the filtration, more described filtrate is carried out sedimentation, washing, drying operation and finally obtain functionalized polyester.
10. preparation method according to claim 9, it is characterized in that described small molecular alcohol or fusing point are lower than 120 ℃ polymeric initiator and the mol ratio of described stannous iso caprylate and described functionalization epoxy compounds and functionalization acid anhydrides is 1: 2000～100000: 5～250: 5～250.
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Non-Patent Citations (2)
| Title |
|---|
| 《chemical communications》 20090807 Feng,lei et al "A novel biodegradable and thermosensitive polymer with PEG-analogue macromolecular structure" 4411-4413 1-9 , 2 * |
| 《macromolecules》 20050614 Bae,SJ et al "Thermogelling poly(caprolactone-b-ethylene glycol-b-caprolactone)aqueous solutions" 5260-5265 5,9 , 2 * |
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| CN115286778A (en) * | 2022-08-31 | 2022-11-04 | 天津大学 | Method for preparing polyester dihydric alcohol by reversible-inactivation ring-opening alternating copolymerization |
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| CN101759845B (en) | 2012-07-11 |
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