CN1887854A - Aniline oligomer, its aliphatic polyester copolymer and their prepn - Google Patents
Aniline oligomer, its aliphatic polyester copolymer and their prepn Download PDFInfo
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- CN1887854A CN1887854A CN 200610016950 CN200610016950A CN1887854A CN 1887854 A CN1887854 A CN 1887854A CN 200610016950 CN200610016950 CN 200610016950 CN 200610016950 A CN200610016950 A CN 200610016950A CN 1887854 A CN1887854 A CN 1887854A
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Abstract
The present invention provides aniline oligomers, their aliphatic polyester copolymer and their preparation. Two kinds of aniline oligomers are first synthesized with N-phenyl-1, 4-p-phenylene diamine as material, and then copolymerized with aliphatic polyester to obtain electrically active biodegradable polymers. During the preparation, N-phenyl-1, 4-p-phenylene diamine has its end amido group protected with butanedioic anhydride and is then reacted with end amido aniline dimer and phenylene diamine to obtain aniline tetramer with one end carboxyl group and one end amino group and aniline pentamer with two end carboxyl groups; and the aniline oligomers are finally polycondensated with double hydroxyl group terminated aliphatic polyester to obtain the copolymers containing electrically active aniline oligomer block. The copolymers possess the advantages of both aniline oligomer and aliphatic polyester, and is used as biomedicine material mainly.
Description
Technical field
The invention belongs to field of biomedical polymer materials, relate to aniline oligomer, itself and aliphatic polyester copolymer and preparation method.
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.Biodegradable Polymers wherein owing to after implanting, do not need second operation to take out, thereby at operating sutures, artificial skin, artificial blood vessel, bone is fixing and repair and fields such as medicine sustained release have obtained widespread use.Biodegradable synthetic macromolecule mainly comprises aliphatic polyester, polyamino acid, poly phosphate, poly-acid anhydrides, poe, polycarbonate etc.Aliphatic polyester, polylactide (PLA) for example, poly-glycollide (PGA), poly-epsilon-caprolactone (PCL) has low immunogenicity and favorable biological degradability and biocompatibility, has been widely used in biomedicine and field of medicaments, as fracture fixation, operating sutures, tissue engineering bracket, the carrier of medicament slow release etc.
Recently, the crossing research in Biodegradable high-molecular and two fields of conducting polymer becomes a focus again.As everyone knows; polyaniline is as a kind of conducting polymer composite; be the focus of a research in recent decades always; because it has controlled specific conductivity; therefore good thermostability and redox property extensively are used as anticorrosion clothing, battery, transmitter, separatory membrane and anti-electrostatic clothing and anti-emi protection screen.But current research shows that electroactive polymer such as polyaniline can be used as a kind of novel intelligent material again and is used as heart or neural timbering material.Basic viewpoint is, electrical signal or electrochemical signals can influence breeding, assembling and the differentiation of cell directly or indirectly, and therefore having electroactive timbering material just can be by being applied in suitable electrical signal to control histiocytic growth and breeding.Recently, (Guterman E. such as crag, Cheng S., Palouian K., Bidez P., Lelkes P., and Wei Y. " the peptide modified electroactive multipolymer that is used for organizational project " .Polym.Prepr.2002,43,766-767) having adopted H9c2 heart sarcoplast and PC12 bladder to have a liking for the chromium tumour cell proves, polyaniline and its derivative can make the good adhesion of cell, growth and differentiation thereon as the substrate material of biocompatibility.Other electroactive polymer when for example polypyrrole also has been proved to be stimulating electrical signal, can be strengthened the influence of nerve growth factor to the Differentiation of PC12 cell.Thereby the application of electroactive polymer material aspect bio-medical caused people's extensive concern, if but electroactive polymers such as polyaniline directly apply to and also exist a lot of problems in the body, such as biocompatibility is poor, and non-degradable and poorly soluble being difficult to process or the like.Round solving said shortcoming more than the electroactive polymer, a series of research work have launched.
In order to improve the biocompatibility of electroactive polymer, a lot of methods have been used, and use at present many to be: and the material blend of biologically active or biocompatible substances and the block that on main polymer chain, connects biocompatibility in the polymer lateral chain grafting.Such as crag etc. are polyaniline and natural biological polymer such as gel (Li, M.; Guo, Y.; Wei, Y.; MacDiarmid, A.G.; Lelkes, P.I. " the polyaniline electricity spinning fibre that contains gel that is used for organizational project " Biomaterials 2006,27 2705-2715.) waits blend, perhaps connect life active compounds such as small peptide, make the biocompatibility of polyaniline be greatly improved at the polyaniline side chain.
Electroactive polymer solvabilities such as polyaniline are generally all poor, can only be dissolved in N, and dinethylformamide is in the intensive polar solvents such as methyl-sulphoxide and N-Methyl pyrrolidone.A lot of problems have been brought for its processed and applied like this.The method that improves the solvability employing of electroactive polymer also is to introduce to increase deliquescent polymkeric substance on polymer lateral chain basically, as polyoxyethylene glycol and polyacrylic acid etc.
The another one important factors that the restriction electroactive polymer is used in vivo is exactly its non-degradable.If electroactive polymers such as polyaniline life-time service in vivo can be induced the untoward reaction of joint inflammation, because its non-degradable uses the back just must to take out by second operation, bring again misery to patient, be the very big drawback of its application.In order to address this problem, the material that needs a person with the qualifications of a general is made can be biodegradable.As (River, T.J. such as Rivers; Hudson, T.W.; Schmidt, C.E. " the biodegradable conductive polymers of synthetic a kind of novelty is used for biomedicine field " .Adv.Funct.Mater.2002,12,33-37) utilize ester bond that pyrroles's oligopolymer is connected with each other and just solved this problem.
Summary of the invention
Also do not have a kind of material can consistency set forth above is poor at present, non-degradable and poorly soluble difficult processing wait all intactly solutions of three shortcomings.In order fundamentally to solve problem set forth above, the contriver generates multipolymer with biodegradable aliphatic polyester and aniline oligomer by ester bond.Aniline oligomer has similar with polyaniline electroactive, and has better solvability, and introduces aliphatic polyester, both can improve biological activity, can solve the problem of degraded again, is a more feasible method.Thereby this multipolymer uses the prospect that provides good for electroactive material in human body, for the nervous tissue engineering materials has been opened up a new road.
One of purpose of the present invention provides the aniline oligomer that has bifunctional group, comprises the aniline tetramer of an end carboxyl one end amino and the aniline pentamer of two carboxy blockings, and their structural formula is respectively:
Two of purpose of the present invention provides the synthetic method of the aniline oligomer that has bifunctional group described in the purpose one, and its synthetic method may further comprise the steps and condition:
1) with N-phenyl-1, the 4-Ursol D is a raw material, and it is dissolved in the methylene dichloride, add and N-phenyl-1 Succinic anhydried of mole numbers such as 4-Ursol D, stirring at room reaction under the nitrogen protection, the gained precipitation to colourless, has obtained the aniline dimer of end amido protecting with the ether washing; Get aniline dimer and two amino-terminated aniline dimer of the end amido protecting of identical mol ratio; be dissolved in the mixed solvent of dimethyl formamide (hereinafter to be referred as DMF) and 1M hydrochloric acid; hydrochloric acid (1M) solution with ammonium persulphate under 0 ℃ of agitation condition dropwise adds; after dropwising; use distilled water wash; to precipitate with behind the ammonia solvent; hydrazine hydrate reduces to it; be 2～3 with the salt acid for adjusting pH value again; with 1; 2-ethylene dichloride and tetrahydrofuran (THF) are distinguished extracting, obtain the aniline tetramer (hereinafter to be referred as AT) of an end carboxyl one end amino.
Its reaction equation is as follows:
2) with above-mentioned 1) hold the dimeric method of aniline of amido protecting the same middle the preparation, obtain holding the aniline dimer of amido protecting earlier; The end aniline dimer of amido protecting and the phenylenediamine mol ratio with 2: 1 is added in the mixed solvent of dimethyl formamide and 1M hydrochloric acid; hydrochloric acid (1M) solution with ammonium persulphate under the stirring at room condition dropwise adds; after dropwising; behind distilled water wash, will precipitate and use ammonia solvent, hydrazine hydrate reduces to it; be 2～3 with the salt acid for adjusting pH value again; with 1,2-ethylene dichloride and tetrahydrofuran (THF) are distinguished extracting, obtain the aniline pentamer (hereinafter to be referred as AP) of two carboxy blockings.Its reaction equation is as follows:
The structure of the aniline pentamer of the aniline tetramer of synthetic one end carboxyl one end amino and two carboxy blockings confirms by substance assistant laser desorpted attached flight time mass spectrum (MALDI-TOF-MS).(seeing Fig. 1 and Fig. 2)
Three of purpose of the present invention is the aniline oligomers with above-mentioned synthetic band bifunctional group, with the two hydroxy-end capped aliphatic polyester that the aliphatics cyclic ester monomer obtains by ring-opening polymerization, polycondensation forms the segmented copolymer of aniline oligomer and aliphatic polyester.The segmented copolymer of aniline oligomer and aliphatic polyester comprises: the aniline tetramer of an end carboxyl one end amino and (AB) n type segmented copolymer of pair aniline tetramer that hydroxy-end capped aliphatic polyester forms and aliphatic polyester and (ABA) n type segmented copolymer of the aniline tetramer and pair hydroxy-end capped aliphatic polyester, n＞2 wherein, A represents the aniline tetramer of an end carboxyl one end amino, and B represents aliphatic polyester; And the aniline pentamer of two carboxy blockings and (AB) n type segmented copolymer of pair aniline pentamer that hydroxy-end capped aliphatic polyester forms and aliphatic polyester and (ABA) n type segmented copolymer of aniline pentamer and pair hydroxy-end capped aliphatic polyester, n＞2 wherein, the two hydroxy-end capped aliphatic polyesters of A representative, the aniline pentamer of the two carboxy blockings of B representative).
Four of purpose of the present invention provides the synthetic method of the segmented copolymer of three described aniline oligomers of purpose and aliphatic polyester.Its step and condition are as follows:
(1) synthetic method of two hydroxy-end capped aliphatic polyesters, its synthetic method may further comprise the steps and condition:
Under the condition of anhydrous and oxygen-free, with toluene is solvent, butyleneglycol is an initiator, and the stannous octoate that adds monomer total mass 1/100～1/1000 in aliphatics cyclic ester monomer (rac-Lactide or 6-caprolactone) is made catalyzer, under heating 100～120oC and stirring condition, polymerization time is 12～72h, product precipitation agent sedimentation is filtered, washing, vacuum-drying obtains the aliphatic polyester that two end groups are hydroxyl; Comprise two hydroxy-end capped polylactides (hereinafter to be referred as PLA) and two hydroxy-end capped poly-epsilon-caprolactone (hereinafter to be referred as PCL).
The synthetic method of (AB) n type segmented copolymer of the aniline tetramer of (2) one end carboxyls one end amino and pair aniline tetramer that hydroxy-end capped aliphatic polyester forms and aliphatic polyester, wherein n＞2; A represents the aniline tetramer of an end carboxyl one end amino, and B represents aliphatic polyester.Its step and condition are:
Earlier with the aniline tetramer (AT) of an end carboxyl one end amino and with its etc. the Succinic anhydried of mole number be dissolved among the DMF, stirring at room 5h under the nitrogen protection settles out with distilled water, drains the aniline tetramer that obtains two carboxy blockings.Then under the condition of anhydrous and oxygen-free, the two hydroxy-end capped aliphatic polyester that makes in the aniline tetramer of two carboxy blockings of mole number and the step (1) such as getting is dissolved in the N-Methyl pyrrolidone (hereinafter to be referred as NMP), the dicyclohexylcarbodiimide (hereinafter to be referred as DCC) that the aniline tetramer mole number of the two carboxy blockings of adding is 2～5 times is made condensing agent, under ice-water bath and stirring condition, reaction 48～72h; Product precipitation agent sedimentation is filtered, washing, and vacuum-drying obtains (AB) n type segmented copolymer of the aniline tetramer of the present invention and aliphatic polyester.Its reaction process is as follows:
The synthetic method of (ABA) n type segmented copolymer of the aniline tetramer of (3) one end carboxyls one end amino and pair aniline tetramer that hydroxy-end capped aliphatic polyester forms and aliphatic polyester, wherein n＞2; A represents the aniline tetramer of an end carboxyl one end amino, and B represents aliphatic polyester.Its step and condition are:
With after the tetrameric amido protecting of aniline of di-tert-butyl dicarbonic acid ester (hereinafter to be referred as (Boc) 20) with an end carboxyl one end amino, obtain the aniline tetramer (hereinafter to be referred as Boc-AT) of an end carboxyl one end amino of tertiary butyl protection earlier.Then under the condition of anhydrous and oxygen-free, the Boc-AT that gets above-mentioned two hydroxy-end capped aliphatic polyester and mole number and be 2 times of the hydroxy-end capped aliphatic polyester of this pair is dissolved among the NMP, the adding mole number is that the DCC of 1～5 times of the hydroxy-end capped aliphatic polyester of this pair makes condensing agent, and under ice-water bath and stirring condition, the reaction times is 48～72h, product precipitation agent sedimentation, filter washing, vacuum-drying, again Boc-is taken off, obtained three block prepolymers of the aniline tetramer and aliphatic polyester.Then under the condition of anhydrous and oxygen-free, in three block prepolymers of the described aniline tetramer and aliphatic polyester 1 of mole number such as adding, 6 hexamethylene diisocyanates (hereinafter to be referred as HDI), the stannous octoate that adds three block prepolymer mole numbers 0.1～1% of the aniline tetramer and aliphatic polyester is made catalyzer, under 55～65oC and the agitation condition, reaction times is 6～12h, product precipitation agent sedimentation, filter, washing, vacuum-drying obtains (ABA) n type segmented copolymer of the aniline tetramer of the present invention and aliphatic polyester.Its reaction process is as follows:
(4) synthetic method of (AB) n type segmented copolymer of the aniline pentamer of two carboxy blockings and pair aniline pentamer that hydroxy-end capped aliphatic polyester forms and aliphatic polyester, wherein n＞2; The two hydroxy-end capped aliphatic polyesters of A representative, the aniline pentamer of the two carboxy blockings of B representative.
Its step and condition are:
Under the condition of anhydrous and oxygen-free, then under the condition of anhydrous and oxygen-free, the aniline tetramer of two carboxy blockings of mole number and above-mentioned two hydroxy-end capped aliphatic polyester such as getting is dissolved among the NMP, the DCC that the aniline pentamer mole number of the two carboxy blockings of adding is 1～5 times makes condensing agent, under ice-water bath and stirring condition, reaction times is 12～72h, product precipitation agent sedimentation, filter, washing, vacuum-drying obtains (AB) n type segmented copolymer of aniline pentamer of the present invention and aliphatic polyester.Its reaction process is as follows:
(5) synthetic method of (ABA) n type segmented copolymer of the aniline pentamer of two carboxy blockings and pair aniline pentamer that hydroxy-end capped aliphatic polyester forms and aliphatic polyester, wherein n＞2; The two hydroxy-end capped aliphatic polyesters of A representative, the aniline pentamer of the two carboxy blockings of B representative.Its step and condition are:
Under the condition of anhydrous and oxygen-free, the two hydroxy-end capped aliphatic polyester of getting 2 times of the aniline pentamer (AP) of two carboxy blockings and aniline pentamers that mole number is this pair carboxy blocking is dissolved among the NMP, the DCC that adds mole number and be 1～5 times of the aniline pentamer of this pair carboxy blocking makes condensing agent, under ice-water bath and stirring condition, reaction times is 12～72h, product precipitation agent sedimentation, filter, washing, vacuum-drying, again Boc-is taken off, obtained three block prepolymers of aniline pentamer and aliphatic polyester.Then under the condition of anhydrous and oxygen-free, the HDI of mole number such as adding in three block prepolymers of the described aniline tetramer and aliphatic polyester, the stannous octoate that adds three block prepolymer mole numbers 0.1～1% of aniline pentamer and aliphatic polyester is made catalyzer, under 55～65oC and the agitation condition, the reaction times is 6～12h, product precipitation agent sedimentation, filter, washing, vacuum-drying obtains (ABA) n type segmented copolymer of aniline pentamer of the present invention and aliphatic polyester.Its reaction process is as follows:
Useful effect of the present invention is as follows:
The present invention is a raw material institute synthetic aniline oligomer with parent aniline dimer, similar oligopolymer with other is compared the advantage that has: have bifunctional group, for being applied in other material copolyreaction generation macromolecule polymkeric substance, it provides precondition, and purity higher (＞99%), highly stable.The multipolymer of aniline oligomer and aliphatic polyester has the good electrical activity similar with polyaniline and aniline oligomer, and had good biocompatibility simultaneously, biodegradable, characteristics such as good solubility, the multipolymer of this aniline oligomer and aliphatic polyester has the biocompatibility similar with polylactide, can support the growth and the differentiation of rat neuroglial cytoma.The film of the multipolymer of aniline oligomer and aliphatic polyester can controlled degradation in containing pepsic phosphoric acid buffer, has good biodegradability.And the multipolymer of this aniline oligomer and aliphatic polyester can be dissolved in most organic solvents, and as chloroform, tetrahydrofuran (THF) etc. are for material processing and utilization in the future provides convenience.
The aniline oligomer that the present invention is prepared and the multipolymer of aliphatic polyester especially are used as the tissue engineering bracket material of nerve and heart mainly as bio-medical material.
Description of drawings
Fig. 1: the tetrameric substance assistant laser desorpted attached flight time mass spectrum of aniline (MALDI-TOF-MS) spectrogram of an end carboxyl one end amino (specifically being the tetrameric substance assistant laser desorpted attached flight time mass spectrum of aniline of an end carboxyl one end amino that obtains among the embodiment 2);
Fig. 2: substance assistant laser desorpted attached flight time mass spectrum (MALDI-TOF-MS) spectrogram of the aniline pentamer of two carboxy blockings (specifically being the substance assistant laser desorpted attached flight time mass spectrum of the aniline pentamer of two carboxy blockings of obtaining among the embodiment 3);
Fig. 3: the proton magnetic resonance (PMR) 1H spectrogram of (AB) n type segmented copolymer of aniline pentamer and aliphatic polyester and ownership (being specially the aniline pentamer that obtains among the embodiment 16 and (AB) n type segmented copolymer proton magnetic resonance (PMR) 1H spectrogram and the ownership of aliphatic polyester polylactide).
Fig. 4: (AB) n type segmented copolymer (n＞2 of the aniline tetramer and aliphatic polyester polylactide, wherein A represents the aniline tetramer of an end carboxyl one end amino, and B represents aliphatic polyester) degradation curve (being specially the degradation curve of embodiment 8 products).
Fig. 5: (AB) n type segmented copolymer (n＞2 of the aniline tetramer and aliphatic polyester polylactide, wherein A represents the aniline tetramer of an end carboxyl one end amino, and B represents aliphatic polyester) biocompatibility result (being specially the biocompatibility result of embodiment 8 products).
Fig. 6: (AB) n type segmented copolymer (n＞2 of the aniline tetramer and aliphatic polyester polylactide, wherein A represents the aniline tetramer of an end carboxyl one end amino, and B represents aliphatic polyester) degradation curve (being specially the degradation curve of embodiment 9 products).
Fig. 7: (AB) n type segmented copolymer (n＞2 of the aniline tetramer and aliphatic polyester polylactide, wherein A represents the aniline tetramer of an end carboxyl one end amino, and B represents aliphatic polyester) biocompatibility result (being specially the biocompatibility result of embodiment 9 products).
Fig. 8: (AB) n type segmented copolymer (n＞2 of the aniline tetramer and aliphatic polyester poly-epsilon-caprolactone, wherein A represents the aniline tetramer of an end carboxyl one end amino, and B represents aliphatic polyester) degradation curve (being specially the degradation curve of embodiment 10 products).
Fig. 9: (AB) n type segmented copolymer (n＞2 of the aniline tetramer and aliphatic polyester poly-epsilon-caprolactone, wherein A represents the aniline tetramer of an end carboxyl one end amino, and B represents aliphatic polyester) biocompatibility result (being specially the biocompatibility result of embodiment 10 products).
Figure 10: (ABA) n type segmented copolymer (n＞2 of the aniline tetramer and aliphatic polyester polylactide, wherein A represents the aniline tetramer of an end carboxyl one end amino, and B represents aliphatic polyester) degradation curve (being specially the degradation curve of embodiment 14 products).
Figure 11: (ABA) n type segmented copolymer (n＞2 of the aniline tetramer and aliphatic polyester polylactide, wherein A represents the aniline tetramer of an end carboxyl one end amino, and B represents aliphatic polyester) biocompatibility result (being specially the biocompatibility result of embodiment 14 products).
Figure 12: (ABA) n type segmented copolymer (n＞2 of the aniline tetramer and aliphatic polyester poly-epsilon-caprolactone, wherein A represents the aniline tetramer of an end carboxyl one end amino, and B represents aliphatic polyester) degradation curve (being specially the degradation curve of embodiment 15 products).
Figure 13: (ABA) n type segmented copolymer (n＞2 of the aniline tetramer and aliphatic polyester poly-epsilon-caprolactone, wherein A represents the aniline tetramer of an end carboxyl one end amino, and B represents aliphatic polyester) biocompatibility result (being specially the biocompatibility result of embodiment 15 products).
Figure 14: the degradation curve (being specially the degradation curve of embodiment 16 products) of (AB) n type segmented copolymer of aniline pentamer and aliphatic polyester polylactide (n＞2, wherein A represents aliphatic polyester, the aniline pentamer of the two carboxy blockings of B representative).
Figure 15: (AB) n type segmented copolymer (n＞2 of aniline pentamer and aliphatic polyester polylactide, wherein A represents aliphatic polyester, the aniline pentamer of the two carboxy blockings of B representative) biocompatibility result (being specially the biocompatibility result of embodiment 16 products).
Figure 16: the degradation curve (being specially the degradation curve of embodiment 17 products) of (AB) n type segmented copolymer of aniline pentamer and aliphatic polyester poly-epsilon-caprolactone (n＞2, wherein A represents aliphatic polyester, the aniline pentamer of the two carboxy blockings of B representative).
Figure 17: (AB) n type segmented copolymer (n＞2 of aniline pentamer and aliphatic polyester poly-epsilon-caprolactone, wherein A represents aliphatic polyester, the aniline pentamer of the two carboxy blockings of B representative) biocompatibility result (being specially the biocompatibility result of embodiment 17 products).
Figure 18: the degradation curve (being specially the degradation curve of embodiment 20 products) of (ABA) n type segmented copolymer of aniline pentamer and aliphatic polyester polylactide (n＞2, wherein A represents aliphatic polyester, the aniline pentamer of the two carboxy blockings of B representative).
Figure 19: (ABA) n type segmented copolymer (n＞2 of aniline pentamer and aliphatic polyester polylactide, wherein A represents aliphatic polyester, the aniline pentamer of the two carboxy blockings of B representative) biocompatibility result (being specially the biocompatibility result of embodiment 20 products).
Figure 20: (ABA) n type segmented copolymer (n＞2 of aniline pentamer and aliphatic polyester poly-epsilon-caprolactone, wherein A represents aliphatic polyester, the aniline pentamer of the two carboxy blockings of B representative) degradation curve (being specially the degradation curve of embodiment 21 products).
Figure 21: (ABA) n type segmented copolymer (n＞2 of aniline pentamer and aliphatic polyester poly-epsilon-caprolactone, wherein A represents aliphatic polyester, the aniline pentamer of the two carboxy blockings of B representative) biocompatibility result (being specially the biocompatibility result of embodiment 21 products).
Embodiment
Below in conjunction with specific examples technical scheme of the present invention is described further.
Embodiment 1: the aniline of end amido protecting is dimeric synthetic
In the there-necked flask of a 500mL that mechanical stirring, nitrogen inlet, nitrogen outlet be housed, add N-phenyl-1,4-Ursol D 9.21g (0.05mol), Succinic anhydried 5.00g (0.05mol), methylene dichloride 300mL stir simultaneously.Carrying out along with reaction produced gray precipitate, after reaction finishes, filters, and the precipitation that obtains is washed with ether, and is colourless up to filtrate.Sample is dry 12h in vacuum drying oven, obtains holding the aniline dimer of amido protecting, productive rate 84.5%.
The aniline of 2: one end carboxyl one end amino of embodiment is tetrameric synthetic
The end aniline dimer 2.85g (0.01mol) of amido protecting and amino end group dimer 3.5g (0.01mol) are dissolved in mixing solutions (comprise 100mlDMF; 15ml distilled water; the 15ml concentrated hydrochloric acid); be cooled to sub-zero zero; hydrochloric acid soln (2.28g is dissolved in the hydrochloric acid of 50ml 1M) with ammonium persulfate slowly adds in the above-mentioned solution by dropping funnel then; stir fast simultaneously; cryosel is kept and is reflected at sub-zero zero; dropwise; continue reaction 2h; then this solution is poured in the 700ml distilled water, filtered.The precipitation that obtains is dissolved in the ammoniacal liquor of 300ml1M, adds hydrazine hydrate N2H4 H2O-100 stirring reduction and spend the night, the hydrochloric acid that adds an amount of 1M then transfers to the ph value and is 2-3, after the filtration, with throw out vacuum-drying 48h under 35 degree.The sample that obtains is first with 1 in apparatus,Soxhlet's, and the 2-ethylene dichloride is used the tetrahydrofuran (THF) extracting again, obtains the aniline tetramer of an end carboxyl one end amino.Its substance assistant laser desorpted attached flight time mass spectrum (MALDI-TOF-MS) spectrogram is seen Fig. 1.
Embodiment 3: two carboxy blocking aniline pentamers synthetic
The aniline dimer 2.85g (0.01mol) and the Ursol D 0.54g (0.005mol) of end amido protecting are dissolved among the 15mL DMF.Adding in advance, refrigerative mixing solutions 60mL (comprises 30mL DMF, 25mL distilled water, the 5mL concentrated hydrochloric acid), hydrochloric acid soln (2.28g is dissolved in the hydrochloric acid of 50mL 1mol/L) with ammonium persulfate slowly adds in the above-mentioned solution by dropping funnel then, stir fast simultaneously, dropwise, continue reaction 1h, then this solution is poured in the 300mL distilled water, filtered.The precipitation that obtains is dissolved in the ammoniacal liquor of 300mL 1mol/L, adds hydrazine hydrate and stir reduction and spend the night, it is 2-3 that the hydrochloric acid that adds an amount of 1mol/L then transfers to pH, after the filtration, with throw out at 45 ℃ of vacuum-drying 48h.The 3.0g sample that obtains is dissolved in 15mL DMF, slowly is added drop-wise to then in the quick ethanol that stirs of 150mL, filter, be deposited under the vacuum and dry, first with 1 in apparatus,Soxhlet's then, the 2-ethylene dichloride, use the tetrahydrofuran (THF) extracting again, obtain two carboxy blocking aniline pentamers, productive rate 84.3%.Its substance assistant laser desorpted attached flight time mass spectrum (MALDI-TOF-MS) spectrogram is seen Fig. 2.
Embodiment 4: molecular weight is the synthetic of 2000 two hydroxy-end capped aliphatic polyester polylactide
Under the condition of anhydrous and oxygen-free, with toluene is solvent, and butyleneglycol is an initiator, and the butyleneglycol that adds monomer molar several 1/25 in the monomer rac-Lactide is made initiator, the stannous octoate of monomer total mass 1/100 is made catalyzer, the heating (100～120oC) and stirring condition under, polymerization time is 12h, product precipitation agent sedimentation, filter, washing, vacuum-drying obtains the homopolymer that two end groups are the polylactide of hydroxyl.
Embodiment 5: molecular weight is the synthetic of 2800 two hydroxy-end capped aliphatic polyester polylactide
Under the condition of anhydrous and oxygen-free, with toluene is solvent, and butyleneglycol is an initiator, and the butyleneglycol that adds monomer molar several 1/12 in the monomer rac-Lactide is made initiator, the stannous octoate of monomer total mass 5/1000 is made catalyzer, the heating (100～120oC) and stirring condition under, polymerization time is 48h, product precipitation agent sedimentation, filter, washing, vacuum-drying obtains the homopolymer that two end groups are the polylactide of hydroxyl.
Embodiment 6: molecular weight is the synthetic of 1500 two hydroxy-end capped aliphatic polyester poly-epsilon-caprolactone
Under the condition of anhydrous and oxygen-free, with toluene is solvent, and butyleneglycol is an initiator, and the butyleneglycol that adds monomer molar several 1/12 in the monomer 6-caprolactone is made initiator, the stannous octoate of monomer total mass 1/1000 is made catalyzer, the heating (100～120oC) and stirring condition under, polymerization time is 72h, product precipitation agent sedimentation, filter, washing, vacuum-drying obtains the homopolymer that two end groups are the poly-epsilon-caprolactone of hydroxyl.
Embodiment 7: two carboxy blockings the aniline tetramer synthetic
Product 5mmol and 5mmol Succinic anhydried that example 2 is obtained are dissolved among the 30mlDMF, and under the nitrogen protection, stirring at room 5h settles out reaction product with 400ml distilled water, suction filtration, and vacuum-drying 48h under the 45oC obtains the aniline tetramer of two carboxy blockings.
Embodiment 8: (AB) n type segmented copolymer of the aniline tetramer and aliphatic polyester polylactide (n＞2, wherein A represents the aniline tetramer of an end carboxyl one end amino, B represents aliphatic polyester) synthetic
Get the aniline tetramer 2mmol of two carboxy blockings that example 7 obtains and molecular weight that example 4 obtains and be 2000 two hydroxy-end capped aliphatic polyester polylactide 2mmol and 4mmolDCC and join in the polyreaction bottle, stirring reaction is 24 hours in the ice-water bath.Product filters insolubles, uses the ether sedimentation, and with the trichloromethane dissolving, the ether sedimentation is filtered again, and 35 ℃ of following vacuum-dryings are to constant weight.Promptly obtain (AB) n type segmented copolymer of the aniline tetramer and aliphatic polyester polylactide.(AB) n type segmented copolymer of this aniline tetramer and aliphatic polyester polylactide has good solubility, can be dissolved in chloroform, acetone, and tetrahydrofuran (THF), methyl-sulphoxide, DMF is in the organic solvents such as NMP.
The comparing result of the gel permeation chromatograph (GPC) of embodiment 8 products and embodiment 4 products has proved the generation of (AB) n type segmented copolymer of this aniline tetramer and aliphatic polyester polylactide in the table one.
| The material title | Mw | Mn | PDI |
| Example 4 products | 2.67×103 | 2.43×103 | 1.09 |
| Example 8 products | 4.32×104 | 3.15×104 | 1.37 |
Table one
Get and spread film after these embodiment 8 products are dissolved in chloroform, obtain the thin slice of 10 * 10 * 0.4mm, place it in the wide-necked bottle that 5ml0.05MTris damping fluid (Proteinase K that contains 60mgL-1) is housed, place 37 ℃ constant temperature vibration case, do not add one time Proteinase K in per 24 hours.At set intervals sample is taken out, give a baby a bath on the third day after its birth time with distilled water, 35 ℃ of vacuum drying ovens are dried to constant weight.Weightlessness before and after the weighing degraded obtains the degradation curve of Fig. 4.This degradation curve has proved that (AB) n type segmented copolymer of the aniline tetramer and aliphatic polyester polylactide is biodegradable.
On the slide glass after the siliconizing, plant the neural keracele C6 of rat cell with embodiment 8 products shop film then in the above, the microscopic examination photo behind the cultivation 48h as shown in Figure 5.(AB) n type segmented copolymer biocompatibility of the adhesion that the C6 cell is good and the growth explanation aniline tetramer and aliphatic polyester polylactide is fine.
Embodiment 9: (AB) n type segmented copolymer of the aniline tetramer and aliphatic polyester polylactide (n＞2, wherein A represents the aniline tetramer of an end carboxyl one end amino, B represents aliphatic polyester) synthetic
Get the aniline tetramer 2mmol of two carboxy blockings that example 7 obtains and molecular weight that 2mmol example 5 obtains and be 2800 two hydroxy-end capped aliphatic polyester polylactide and 10mmolDCC and join in the polyreaction bottle, stirring reaction is 72 hours in the ice-water bath.Product filters insolubles, uses the ether sedimentation, and with the trichloromethane dissolving, the ether sedimentation is filtered again, and 35 ℃ of following vacuum-dryings are to constant weight.Promptly obtain (AB) n type segmented copolymer of the aniline tetramer and aliphatic polyester polylactide.(AB) n type segmented copolymer of this aniline tetramer and aliphatic polyester polylactide has good solubility, can be dissolved in chloroform, acetone, and tetrahydrofuran (THF), methyl-sulphoxide, DMF is in the organic solvents such as NMP.
The comparing result of the gel permeation chromatograph (GPC) of example 9 products and embodiment 5 products has proved the generation of (AB) n type segmented copolymer of this aniline tetramer and aliphatic polyester polylactide in the table two.
| The material title | Mw | Mn | PDI |
| Example 5 products | 3.15×103 | 2.86×103 | 1.10 |
| Example 9 products | 6.56×104 | 5.12×104 | 1.28 |
Table two
Get and spread film after these embodiment 9 products are dissolved in chloroform, obtain the thin slice of 10 * 10 * 0.4mm, place it in the wide-necked bottle that 5ml0.05MTris damping fluid (Proteinase K that contains 60mgL-1) is housed, place 37 ℃ constant temperature vibration case, do not add one time Proteinase K in per 24 hours.At set intervals sample is taken out, give a baby a bath on the third day after its birth time with distilled water, 35 ℃ of vacuum drying ovens are dried to constant weight.Weightlessness before and after the weighing degraded obtains the degradation curve of Fig. 6.This degradation curve has proved that (AB) n type segmented copolymer of the aniline tetramer and aliphatic polyester polylactide is biodegradable.
On the slide glass after the siliconizing, plant the neural keracele C6 of rat cell with embodiment 9 products shop film then in the above, the microscopic examination photo behind the cultivation 48h as shown in Figure 7.(AB) n type segmented copolymer biocompatibility of the adhesion that the C6 cell is good and the growth explanation aniline tetramer and aliphatic polyester polylactide is fine.
Embodiment 10: (AB) n type segmented copolymer of the aniline tetramer and aliphatic polyester poly-epsilon-caprolactone (n＞2, wherein A represents the aniline tetramer of an end carboxyl one end amino, B represents aliphatic polyester) synthetic
Get the aniline tetramer 2mmol of two carboxy blockings that example 7 obtains and molecular weight that 2mmol example 6 obtains and be 1500 two hydroxy-end capped aliphatic polyester poly-epsilon-caprolactone and 8mmolDCC and join in the polyreaction bottle, stirring reaction is 56 hours in the ice-water bath.Product filters insolubles, uses the ether sedimentation, and with the trichloromethane dissolving, the ether sedimentation is filtered again, and 35 ℃ of following vacuum-dryings are to constant weight.Promptly obtain (AB) n type segmented copolymer of the aniline tetramer and aliphatic polyester polylactide.(AB) n type segmented copolymer of this aniline tetramer and aliphatic polyester polylactide has good solubility, can be dissolved in chloroform, acetone, and tetrahydrofuran (THF), methyl-sulphoxide, DMF is in the organic solvents such as NMP.
The comparing result of the gel permeation chromatograph (GPC) of example 10 products and embodiment 6 products has proved the generation of (AB) n type segmented copolymer of this aniline tetramer and aliphatic polyester poly-epsilon-caprolactone in the table three.
| The material title | Mw | Mn | PDI |
| Example 6 products | 1.80×103 | 1.71×103 | 1.05 |
| Example 10 products | 6.56×104 | 5.12×104 | 1.28 |
Table three
Get and spread film after these embodiment 10 products are dissolved in chloroform, obtain the thin slice of 10 * 10 * 0.4mm, place it in the wide-necked bottle that 5ml0.05MTris damping fluid (Proteinase K that contains 60mgL-1) is housed, place 37 ℃ constant temperature vibration case, do not add one time Proteinase K in per 24 hours.At set intervals sample is taken out, give a baby a bath on the third day after its birth time with distilled water, 35 ℃ of vacuum drying ovens are dried to constant weight.Weightlessness before and after the weighing degraded obtains the degradation curve of Fig. 8.This degradation curve has proved that (AB) n type segmented copolymer of the aniline tetramer and aliphatic polyester poly-epsilon-caprolactone is biodegradable.
On the slide glass after the siliconizing, plant the neural keracele C6 of rat cell with embodiment 9 products shop film then in the above, the microscopic examination photo behind the cultivation 48h as shown in Figure 9.(AB) n type segmented copolymer biocompatibility of the adhesion that the C6 cell is good and the growth explanation aniline tetramer and aliphatic polyester poly-epsilon-caprolactone is fine.
Synthesizing of the aniline tetramer (Boc-AT) of one end carboxyl, the one end amino of embodiment 11:Boc protection
Get the aniline tetramer (AT) 5mmol and 5.5mmol (Boc) 20 and the 30mlDMF mixing of an end carboxyl one end amino that obtains in the example 2; 6h is stirred in nitrogen protection down; then with 400ml distilled water precipitation; filter; with washed with dichloromethane 3 times; vacuum-drying obtains the aniline tetramer (Boc-AT) of Boc protection to constant weight under the room temperature.
Embodiment 12: three block prepolymers (AT-PLA-AT) of the aniline tetramer and aliphatic polyester polylactide synthetic
Get the aniline tetramer (Boc-AT) 2.5mmol of the Boc protection that obtains in the example 11 and two hydroxy-end capped polylactide and 5mmolDCC that 1mmol embodiment 4 obtains and join in the polyreaction bottle, stirring reaction is 24 hours in the ice-water bath.Product filters insolubles, uses the ether sedimentation, and with the trichloromethane dissolving, the ether sedimentation is filtered again, and 35 ℃ of following vacuum-dryings add trifluoroacetic acid and the 30mlDMF of 20mmol again to constant weight in products therefrom, under the room temperature, and stirring reaction 2h.Products therefrom concentrates the back and uses ether sedimentation, and 35 ℃ of following vacuum-dryings are to constant weight.Promptly obtain three block prepolymers (AT-PLA-AT) of the aniline tetramer and aliphatic polyester polylactide.
The result of the gel permeation chromatograph (GPC) of example 12 products and embodiment 4 products contrast can prove the generation of three block prepolymers of the aniline tetramer and aliphatic polyester polylactide in the table four.
| The material title | Mw | Mn | PDI |
| Example 4 products | 2.67×103 | 2.43×103 | 1.09 |
| Example 12 products | 3.63×103 | 3.30×103 | 1.10 |
Table four
Embodiment 13: three block prepolymers (AT-PCL-AT) of the aniline tetramer and aliphatic polyester poly-epsilon-caprolactone synthetic
Get the aniline tetramer (Boc-AT) 2.5mmol of the Boc protection that obtains among the embodiment 11 and two hydroxy-end capped poly-epsilon-caprolactone and 10mmolDCC that 1mmol embodiment 6 obtains and join in the polyreaction bottle, stirring reaction is 48 hours in the ice-water bath.Product filters insolubles, uses the ether sedimentation, and with the trichloromethane dissolving, the ether sedimentation is filtered again, and 35 ℃ of following vacuum-dryings add trifluoroacetic acid and the 30mlDMF of 20mmol again to constant weight in products therefrom, under the room temperature, and stirring reaction 2h.Products therefrom concentrates the back and uses ether sedimentation, and 35 ℃ of following vacuum-dryings are to constant weight.Promptly obtain three block prepolymers (AT-PCL-AT) of the aniline tetramer and aliphatic polyester poly-epsilon-caprolactone.
The result of the gel permeation chromatograph (GPC) of example 13 products and embodiment 6 products contrast can prove the generation of three block prepolymers of the aniline tetramer and aliphatic polyester poly-epsilon-caprolactone in the table five.
| The material title | Mw | Mn | PDI |
| Example 6 products | 1.80×103 | 1.71×103 | 1.05 |
| Example 13 products | 2.73×103 | 2.55×103 | 1.07 |
Table five
Embodiment 14: (ABA) n type segmented copolymer of the aniline tetramer and aliphatic polyester polylactide (n＞2, wherein A represents the aniline tetramer of an end carboxyl one end amino, B represents aliphatic polyester) synthetic
Under the condition of anhydrous and oxygen-free, get the aniline tetramer that obtains among the embodiment 12 and three block prepolymer 0.001mol of aliphatic polyester polylactide and the diphenylmethanediisocyanate (MDI) of 0.001mol and be dissolved in 20ml toluene, add the 0.01mmol stannous octoate again, under 55 ℃, vigorous stirring reaction 6 hours.Reaction product ether sedimentation is filtered, and 35 ℃ of following vacuum-dryings promptly obtain (ABA) n type segmented copolymer of the aniline tetramer and aliphatic polyester polylactide to constant weight.(ABA) n type segmented copolymer of this aniline tetramer and aliphatic polyester polylactide has good solubility, can be dissolved in chloroform, acetone, and tetrahydrofuran (THF), methyl-sulphoxide, DMF is in the organic solvents such as NMP.
The result of the gel permeation chromatograph (GPC) of example 14 products and embodiment 12 products contrast can prove the generation of (ABA) n type segmented copolymer of this aniline tetramer and aliphatic polyester polylactide in the table six.
| The material title | Mw | Mn | PDI |
| Example 12 products | 3.63×103 | 3.30×103 | 1.10 |
| Example 14 products | 5.72×104 | 4.73×104 | 1.21 |
Table six
Get and spread film after these embodiment 14 products are dissolved in chloroform, obtain the thin slice of 10 * 10 * 0.4mm, place it in the wide-necked bottle that 5ml0.05MTris damping fluid (Proteinase K that contains 60mgL-1) is housed, place 37 ℃ constant temperature vibration case, do not add one time Proteinase K in per 24 hours.At set intervals sample is taken out, give a baby a bath on the third day after its birth time with distilled water, 35 ℃ of vacuum drying ovens are dried to constant weight.Weightlessness before and after the weighing degraded obtains the degradation curve of Figure 10.This degradation curve has proved that (ABA) n type segmented copolymer of the aniline tetramer and aliphatic polyester polylactide is biodegradable.
On the slide glass after the siliconizing, plant the neural keracele C6 of rat cell with embodiment 14 products shop film then in the above, the microscopic examination photo behind the cultivation 48h as shown in figure 11.(ABA) n type segmented copolymer biocompatibility of the adhesion that the C6 cell is good and the growth explanation aniline aniline tetramer and aliphatic polyester polylactide is fine.
Embodiment 15: (ABA) n type segmented copolymer of the aniline tetramer and aliphatic polyester poly-epsilon-caprolactone (n＞2, wherein A represents the aniline tetramer of an end carboxyl one end amino, B represents aliphatic polyester) synthetic
Under the condition of anhydrous and oxygen-free, get the aniline tetramer that obtains among the embodiment 13 and three block prepolymer 0.001mol of aliphatic polyester poly-epsilon-caprolactone and the diphenylmethanediisocyanate (MDI) of 0.001mol and be dissolved in 20ml toluene, add the 0.001mmol stannous octoate again, under 60 ℃, vigorous stirring reaction 12 hours.Reaction product ether sedimentation is filtered, and 35 ℃ of following vacuum-dryings promptly obtain (ABA) n type segmented copolymer of the aniline tetramer and aliphatic polyester poly-epsilon-caprolactone to constant weight.(ABA) n type segmented copolymer of this aniline tetramer and aliphatic polyester poly-epsilon-caprolactone has good solubility, can be dissolved in chloroform, acetone, and tetrahydrofuran (THF), methyl-sulphoxide, DMF is in the organic solvents such as NMP.
The result of the gel permeation chromatograph (GPC) of (ABA) n type segmented copolymer of this aniline tetramer and aliphatic polyester poly-epsilon-caprolactone and embodiment 12 products contrast can prove the generation of (ABA) n type segmented copolymer of the aniline tetramer and aliphatic polyester poly-epsilon-caprolactone in the table seven.
| The material title | Mw | Mn | PDI |
| Example 13 products | 2.73×103 | 2.55×103 | 1.07 |
| Example 15 products | 4.32×104 | 36.3×104 | 1.19 |
Table seven
Get and spread film after these embodiment 15 products are dissolved in chloroform, obtain the thin slice of 10 * 10 * 0.4mm, place it in the wide-necked bottle that 5ml0.05MTris damping fluid (Proteinase K that contains 60mgL-1) is housed, place 37 ℃ constant temperature vibration case, do not add one time Proteinase K in per 24 hours.At set intervals sample is taken out, give a baby a bath on the third day after its birth time with distilled water, 35 ℃ of vacuum drying ovens are dried to constant weight.Weightlessness before and after the weighing degraded obtains the degradation curve of Figure 12.This degradation curve has proved that (ABA) n type segmented copolymer of the aniline tetramer and aliphatic polyester poly-epsilon-caprolactone is biodegradable.
On the slide glass after the siliconizing, plant the neural keracele C6 of rat cell with embodiment 15 products shop film then in the above, the microscopic examination photo behind the cultivation 48h as shown in figure 13.(ABA) n type segmented copolymer biocompatibility of the adhesion that the C6 cell is good and the growth explanation aniline tetramer and aliphatic polyester poly-epsilon-caprolactone is fine.
Embodiment 16: (AB) n type segmented copolymer of aniline pentamer and aliphatic polyester polylactide (n＞2, wherein A represents aliphatic polyester, the aniline pentamer of the two carboxy blockings of B representative) synthetic
Under the condition of anhydrous and oxygen-free, the aniline pentamer (AP) of the two carboxy blockings of the 1mmol that obtains among the embodiment 3 and two hydroxy-end capped polylactide and the 5mmolDCC that 1mmol embodiment 5 obtains are joined in the polyreaction bottle, and stirring reaction is 36 hours in the ice-water bath.Product filters insolubles, uses the ether sedimentation, and with the trichloromethane dissolving, the ether sedimentation is filtered again, and 35 ℃ of following vacuum-dryings promptly obtain (AB) n type segmented copolymer of aniline pentamer and aliphatic polyester polylactide to constant weight.(AB) n type segmented copolymer of this aniline pentamer and aliphatic polyester polylactide has good solubility, can be dissolved in chloroform, acetone, and tetrahydrofuran (THF), methyl-sulphoxide, DMF is in the organic solvents such as NMP.
The comparing result of the gel permeation chromatograph (GPC) of example 16 products and embodiment 5 products has proved the generation of (AB) n type segmented copolymer of aniline pentamer and aliphatic polyester polylactide in the table eight.
| The material title | Mw | Mn | PDI |
| Example 5 products | 3.15×103 | 2.86×103 | 1.10 |
| Example 16 products | 8.43×104 | 7.04×104 | 1.20 |
Table eight
Get and spread film after these embodiment 16 products are dissolved in chloroform, obtain the thin slice of 10 * 10 * 0.4mm, place it in the wide-necked bottle that 5ml0.05MTris damping fluid (Proteinase K that contains 60mgL-1) is housed, place 37 ℃ constant temperature vibration case, do not add one time Proteinase K in per 24 hours.At set intervals sample is taken out, give a baby a bath on the third day after its birth time with distilled water, 35 ℃ of vacuum drying ovens are dried to constant weight.Weightlessness before and after the weighing degraded obtains the degradation curve of Figure 14.This degradation curve has proved that (AB) n type segmented copolymer of aniline pentamer and aliphatic polyester polylactide is biodegradable.
On the slide glass after the siliconizing, plant the neural keracele C6 of rat cell with embodiment 16 products shop film then in the above, the microscopic examination photo behind the cultivation 48h as shown in figure 15.(AB) n type segmented copolymer biocompatibility of the adhesion that the C6 cell is good and growth explanation aniline pentamer and aliphatic polyester polylactide is fine.
Embodiment 17: (AB) n type segmented copolymer of aniline pentamer and aliphatic polyester poly-epsilon-caprolactone (n＞2, wherein A represents aliphatic polyester, the aniline pentamer of the two carboxy blockings of B representative) synthetic
Under the condition of anhydrous and oxygen-free, the aniline pentamer (AP) of the two carboxy blockings of the 1mmol that obtains among the embodiment 3 and two hydroxy-end capped poly-epsilon-caprolactone and the 3mmolDCC that 1mmol embodiment 6 obtains are joined in the polyreaction bottle, and stirring reaction is 48 hours in the ice-water bath.Product filters insolubles, uses the ether sedimentation, and with the trichloromethane dissolving, the ether sedimentation is filtered again, and 35 ℃ of following vacuum-dryings promptly obtain (AB) n type segmented copolymer of aniline pentamer and aliphatic polyester poly-epsilon-caprolactone to constant weight.(AB) n type segmented copolymer of this aniline pentamer and aliphatic polyester poly-epsilon-caprolactone has good solubility, can be dissolved in chloroform, acetone, and tetrahydrofuran (THF), methyl-sulphoxide, DMF is in the organic solvents such as NMP.
The comparing result of the gel permeation chromatograph (GPC) of example 17 products and embodiment 6 products has proved the generation of (AB) n type segmented copolymer of aniline pentamer and aliphatic polyester poly-epsilon-caprolactone in the table nine.
| The material title | Mw | Mn | PDI |
| Example 6 products | 1.80×103 | 1.71×103 | 1.05 |
| Example 17 products | 4.83×104 | 4.43×104 | 1.09 |
Table nine
Get and spread film after these embodiment 17 products are dissolved in chloroform, obtain the thin slice of 10 * 10 * 0.4mm, place it in the wide-necked bottle that 5ml0.05MTris damping fluid (Proteinase K that contains 60mgL-1) is housed, place 37 ℃ constant temperature vibration case, do not add one time Proteinase K in per 24 hours.At set intervals sample is taken out, give a baby a bath on the third day after its birth time with distilled water, 35 ℃ of vacuum drying ovens are dried to constant weight.Weightlessness before and after the weighing degraded obtains the degradation curve of Figure 16.This degradation curve has proved that (AB) n type segmented copolymer of aniline pentamer and aliphatic polyester poly-epsilon-caprolactone is biodegradable.
On the slide glass after the siliconizing, plant the neural keracele C6 of rat cell with embodiment 17 products shop film then in the above, the microscopic examination photo behind the cultivation 48h as shown in figure 17.(AB) n type segmented copolymer biocompatibility of the adhesion that the C6 cell is good and growth explanation aniline pentamer and aliphatic polyester poly-epsilon-caprolactone is fine.
Embodiment 18: three block prepolymers of aniline pentamer and aliphatic polyester polylactide synthetic
Under the condition of anhydrous and oxygen-free, with aniline pentamer (AP) 1mmol of two carboxy blockings of obtaining among the embodiment 3 and two hydroxy-end capped polylactide and 5mmolDCC that 2mmol embodiment 4 obtains, join in the polyreaction bottle, stirring reaction is 48 hours in the ice-water bath.Product filters insolubles, uses the ether sedimentation, and with the trichloromethane dissolving, the ether sedimentation is filtered again, and 35 ℃ of following vacuum-dryings promptly obtain three block prepolymers of aniline pentamer and aliphatic polyester polylactide to constant weight.
The result of the gel permeation chromatograph (GPC) of example 18 products and embodiment 4 products contrast can prove the generation of three block prepolymers of aniline pentamer and aliphatic polyester polylactide in the table ten.
| The material title | Mw | Mn | PDI |
| Example 4 products | 2.67×103 | 2.43×103 | 1.09 |
| Example 18 products | 5.73×103 | 5.07×103 | 1.13 |
Table ten
Embodiment 19: three block prepolymers of aniline pentamer and aliphatic polyester poly-epsilon-caprolactone synthetic
Under the condition of anhydrous and oxygen-free, with the aniline pentamer (AP) of the two carboxy blockings of the 1mmol that obtains among the embodiment 3 and two hydroxy-end capped poly-epsilon-caprolactone and 2.5mmolDCC that 2mmol embodiment 6 obtains, join in the polyreaction bottle, stirring reaction is 24 hours in the ice-water bath.Product filters insolubles, uses the ether sedimentation, and with the trichloromethane dissolving, the ether sedimentation is filtered again, and 35 ℃ of following vacuum-dryings promptly obtain three block prepolymers of aniline pentamer and aliphatic polyester poly-epsilon-caprolactone to constant weight.
The result of the gel permeation chromatograph (GPC) of example 19 products and embodiment 4 products contrast can prove the generation of three block prepolymers of aniline pentamer and aliphatic polyester poly-epsilon-caprolactone in the table ten one.
| The material title | Mw | Mn | PDI |
| Example 5 products | 1.80×103 | 1.71×103 | 1.05 |
| Example 19 products | 4.54×103 | 3.69×103 | 1.23 |
Table ten one
Embodiment 20: (ABA) n type segmented copolymer of aniline pentamer and aliphatic polyester polylactide (n＞2, wherein A represents aliphatic polyester, the aniline pentamer of the two carboxy blockings of B representative) synthetic
Under the condition of anhydrous and oxygen-free, get aniline pentamer that embodiment 18 obtained and three block prepolymer 1mmol of aliphatic polyester polylactide and the diphenylmethanediisocyanate (MDI) of 1mmol and be dissolved in 20ml toluene, add the 0.05mmol stannous octoate again, under 55 ℃, vigorous stirring reaction 12 hours.Reaction product ether sedimentation is filtered, and 35 ℃ of following vacuum-dryings promptly obtain (ABA) n type segmented copolymer of aniline pentamer and aliphatic polyester polylactide to constant weight.(ABA) n type segmented copolymer of this aniline pentamer and aliphatic polyester polylactide has good solubility, can be dissolved in chloroform, acetone, and tetrahydrofuran (THF), methyl-sulphoxide, DMF is in the organic solvents such as NMP.
The result of the gel permeation chromatograph (GPC) of example 20 products and embodiment 18 products contrast can prove the generation of (ABA) n type segmented copolymer of aniline pentamer and aliphatic polyester polylactide in the table ten two.
| The material title | Mw | Mn | PDI |
| Example 18 products | 5.73×103 | 5.07×103 | 1.13 |
| Example 20 products | 5.45×104 | 4.36×104 | 1.25 |
Table ten two
Get and spread film after these embodiment 20 products are dissolved in chloroform, obtain the thin slice of 10 * 10 * 0.4mm, place it in the wide-necked bottle that 5ml0.05MTris damping fluid (Proteinase K that contains 60mgL-1) is housed, place 37 ℃ constant temperature vibration case, do not add one time Proteinase K in per 24 hours.At set intervals sample is taken out, give a baby a bath on the third day after its birth time with distilled water, 35 ℃ of vacuum drying ovens are dried to constant weight.Weightlessness before and after the weighing degraded obtains the degradation curve of Figure 18.This degradation curve has proved that (ABA) n type segmented copolymer of aniline pentamer and aliphatic polyester polylactide is biodegradable.
On the slide glass after the siliconizing, plant the neural keracele C6 of rat cell with embodiment 20 products shop film then in the above, the microscopic examination photo behind the cultivation 48h as shown in figure 19.(ABA) n type segmented copolymer biocompatibility of the adhesion that the C6 cell is good and growth explanation aniline pentamer and aliphatic polyester polylactide is fine.
Embodiment 21: (ABA) n type segmented copolymer of aniline pentamer and aliphatic polyester 6-caprolactone (n＞2,
Wherein A represents aliphatic polyester, the aniline pentamer of the two carboxy blockings of B representative) synthetic
Under the condition of anhydrous and oxygen-free, get aniline pentamer that embodiment 19 obtained and three block prepolymer 1mmol of aliphatic polyester poly-epsilon-caprolactone and the diphenylmethanediisocyanate (MDI) of 1mmol and be dissolved in 20ml toluene, add the 0.01mmol stannous octoate again, under 60 ℃, vigorous stirring reaction 10 hours.Reaction product ether sedimentation is filtered, and 35 ℃ of following vacuum-dryings promptly obtain (ABA) n type segmented copolymer of aniline pentamer and aliphatic polyester poly-epsilon-caprolactone to constant weight.(ABA) n type segmented copolymer of this aniline pentamer and aliphatic polyester poly-epsilon-caprolactone has good solubility, can be dissolved in chloroform, acetone, and tetrahydrofuran (THF), methyl-sulphoxide, DMF is in the organic solvents such as NMP.
The result of the gel permeation chromatograph (GPC) of example 21 products and embodiment 18 products contrasts the generation that has proved (ABA) of aniline pentamer and aliphatic polyester 6-caprolactone n type segmented copolymer in the table ten three.
| The material title | Mw | Mn | PDI |
| Example 19 products | 4.54×103 | 3.69×103 | 1.23 |
| Example 21 products | 5.17×104 | 4.04×104 | 1.28 |
Table ten three
Get and spread film after these embodiment 21 products are dissolved in chloroform, obtain the thin slice of 10 * 10 * 0.4mm, place it in the wide-necked bottle that 5ml0.05MTris damping fluid (Proteinase K that contains 60mgL-1) is housed, place 37 ℃ constant temperature vibration case, do not add one time Proteinase K in per 24 hours.At set intervals sample is taken out, give a baby a bath on the third day after its birth time with distilled water, 35 ℃ of vacuum drying ovens are dried to constant weight.Weightlessness before and after the weighing degraded obtains following degradation curve.This degradation curve has proved that (ABA) n type segmented copolymer of aniline pentamer and aliphatic polyester 6-caprolactone is biodegradable.
On the slide glass after the siliconizing, plant the neural keracele C6 of rat cell with embodiment 21 products shop film then in the above, the microscopic examination photo behind the cultivation 48h is as follows.(ABA) n type segmented copolymer biocompatibility of the adhesion that the C6 cell is good and growth explanation aniline pentamer and aliphatic polyester 6-caprolactone is fine.
Claims (10)
1. an aniline oligomer is characterized in that, this oligopolymer is the aniline tetramer of an end carboxyl one end amino or the aniline pentamer of two carboxy blockings, and following two formulas are respectively its structural formula.
2. the segmented copolymer of aniline oligomer as claimed in claim 1 and aliphatic polyester, it is characterized in that this segmented copolymer is: the aniline tetramer of an end carboxyl one end amino and pair aniline tetramer that hydroxy-end capped aliphatic polyester forms and (AB) n type segmented copolymer of aliphatic polyester; N＞2 wherein, A represents the aniline tetramer of an end carboxyl one end amino, and it is to obtain the homopolymer that two end groups are hydroxyl by aliphatics cyclic ester monomer rac-Lactide or 6-caprolactone by ring-opening polymerization that B represents aliphatic polyester.
3. the segmented copolymer of aniline oligomer as claimed in claim 1 and aliphatic polyester, it is characterized in that this segmented copolymer is: the aniline tetramer of an end carboxyl one end amino and pair aniline tetramer that hydroxy-end capped aliphatic polyester forms and (ABA) n type segmented copolymer of aliphatic polyester; N＞2 wherein, A represents the aniline tetramer of an end carboxyl one end amino, and it is to obtain the homopolymer that two end groups are hydroxyl by aliphatics cyclic ester monomer rac-Lactide or 6-caprolactone by ring-opening polymerization that B represents aliphatic polyester.
4. the segmented copolymer of aniline oligomer as claimed in claim 1 and aliphatic polyester, it is characterized in that this segmented copolymer is: the aniline pentamer of two carboxy blockings and pair aniline pentamer that hydroxy-end capped aliphatic polyester forms and (AB) n type segmented copolymer of aliphatic polyester; N＞2 wherein, the two hydroxy-end capped aliphatic polyesters of A representative are to obtain the homopolymer that two end groups are hydroxyl by aliphatics cyclic ester monomer rac-Lactide or 6-caprolactone by ring-opening polymerization, the aniline pentamer of the two carboxy blockings of B representative.
5. the segmented copolymer of aniline oligomer as claimed in claim 1 and aliphatic polyester, it is characterized in that, this segmented copolymer is: (ABA) n type segmented copolymer of the aniline pentamer of two carboxy blockings and aliphatic polyester, n＞2 wherein, the two hydroxy-end capped aliphatic polyesters of A representative are to obtain the homopolymer that two end groups are hydroxyl by aliphatics cyclic ester monomer rac-Lactide or 6-caprolactone by ring-opening polymerization, the aniline pentamer of the two carboxy blockings of B representative.
6. the preparation method of a kind of aniline oligomer as claimed in claim 1 is characterized in that, step and condition are:
1) with N-phenyl-1, the 4-Ursol D is a raw material, and it is dissolved in the methylene dichloride, add and N-phenyl-1 Succinic anhydried of mole numbers such as 4-Ursol D, stirring at room reaction under the nitrogen protection, the gained precipitation to colourless, has obtained the aniline dimer of end amido protecting with the ether washing; Get aniline dimer and two amino-terminated aniline dimer of the end amido protecting of identical mol ratio, be dissolved in the mixed solvent of dimethyl formamide and 1M hydrochloric acid, 1M hydrochloric acid soln with ammonium persulphate under 0 ℃ of agitation condition dropwise adds, and after dropwising, uses distilled water wash, to precipitate with behind the ammonia solvent, hydrazine hydrate reduces to it, is 2～3 with the salt acid for adjusting pH value again, with 1,2-ethylene dichloride and tetrahydrofuran (THF) are distinguished extracting, obtain the aniline tetramer of an end carboxyl one end amino;
2) with above-mentioned 1) hold the dimeric method of aniline of amido protecting the same middle the preparation, obtain holding the aniline dimer of amido protecting earlier; The end aniline dimer of amido protecting and the phenylenediamine mol ratio with 2: 1 is added in the mixed solvent of dimethyl formamide and 1M hydrochloric acid; 1M hydrochloric acid soln with ammonium persulphate under the stirring at room condition dropwise adds; after dropwising; behind distilled water wash, will precipitate and use ammonia solvent, hydrazine hydrate reduces to it; be 2～3 with the salt acid for adjusting pH value again; with 1,2-ethylene dichloride and tetrahydrofuran (THF) are distinguished extracting, obtain the aniline pentamer of two carboxy blockings.
7. a kind of aniline oligomer as claimed in claim 2 and aliphatic polyester the preparation method of many blocks (AB) n type multipolymer, it is characterized in that step and condition are:
(1) step and the condition of the synthetic method of two hydroxy-end capped aliphatic polyesters:
Under the condition of anhydrous and oxygen-free, with toluene is solvent, butyleneglycol is an initiator, and to the aliphatics cyclic ester monomer: the stannous octoate that adds monomer total mass 1/100～1/1000 in rac-Lactide or the 6-caprolactone is made catalyzer, under 100～120 ℃ of heating and stirring condition, polymerization time is 12～72h, product precipitation agent sedimentation is filtered, washing, vacuum-drying obtains the aliphatic polyester that two end groups are hydroxyl; Comprise two hydroxy-end capped polylactides and two hydroxy-end capped poly-epsilon-caprolactone;
(2) earlier with the aniline tetramer of an end carboxyl one end amino and with its etc. the Succinic anhydried of mole number be dissolved in the dimethyl formamide, stirring at room 5h under the nitrogen protection settles out with distilled water, drains the aniline tetramer that obtains two carboxy blockings; Then under the condition of anhydrous and oxygen-free, the two hydroxy-end capped aliphatic polyester that makes in the aniline tetramer of two carboxy blockings of mole number and the step (1) such as getting is dissolved in the N-Methyl pyrrolidone, the dicyclohexylcarbodiimide that the aniline tetramer mole number of the two carboxy blockings of adding is 2～5 times is made condensing agent, under ice-water bath and stirring condition, reaction 48～72h; Product precipitation agent sedimentation is filtered, washing, and vacuum-drying obtains (AB) n type segmented copolymer of the aniline tetramer of the present invention and aliphatic polyester.
8. a kind of aniline oligomer as claimed in claim 3 and aliphatic polyester the preparation method of many blocks (ABA) n type multipolymer, it is characterized in that step and condition are:
(1) step and the condition of the synthetic method of two hydroxy-end capped aliphatic polyesters:
Under the condition of anhydrous and oxygen-free, with toluene is solvent, butyleneglycol is an initiator, and to the aliphatics cyclic ester monomer: the stannous octoate that adds monomer total mass 1/100～1/1000 in rac-Lactide or the 6-caprolactone is made catalyzer, under 100～120 ℃ of heating and stirring condition, polymerization time is 12～72h, product precipitation agent sedimentation is filtered, washing, vacuum-drying obtains the aliphatic polyester that two end groups are hydroxyl; Comprise two hydroxy-end capped polylactides and two hydroxy-end capped poly-epsilon-caprolactone;
(2), obtain the aniline tetramer of an end carboxyl one end amino of tertiary butyl protection earlier with after the tetrameric amido protecting of aniline of di-tert-butyl dicarbonic acid ester with an end carboxyl one end amino; Then under the condition of anhydrous and oxygen-free, the aniline tetramer of an end carboxyl one end amino of getting above-mentioned two hydroxy-end capped aliphatic polyester and mole number and be the tertiary butyl protection of 2 times of the hydroxy-end capped aliphatic polyester of this pair is dissolved in the N-Methyl pyrrolidone, the adding mole number is that the dicyclohexylcarbodiimide of 1～5 times of the hydroxy-end capped aliphatic polyester of this pair is made condensing agent, under ice-water bath and stirring condition, reaction times is 48～72h, product precipitation agent sedimentation, filter, washing, vacuum-drying, again the tertiary butyl is taken off, obtained three block prepolymers of the aniline tetramer and aliphatic polyester; Then under the condition of anhydrous and oxygen-free, in three block prepolymers of the described aniline tetramer and aliphatic polyester 1 of mole number such as adding, 6 hexamethylene diisocyanates, the stannous octoate that adds three block prepolymer mole numbers 0.1～1% of the aniline tetramer and aliphatic polyester is made catalyzer, under 55～65 ℃ and the agitation condition, reaction times is 6～12h, product precipitation agent sedimentation, filter, washing, vacuum-drying obtains (ABA) n type segmented copolymer of the aniline tetramer of the present invention and aliphatic polyester.
9. a kind of aniline oligomer as claimed in claim 4 and aliphatic polyester the preparation method of many blocks (AB) n type multipolymer, it is characterized in that step and condition are:
(1) step and the condition of the synthetic method of two hydroxy-end capped aliphatic polyesters:
Under the condition of anhydrous and oxygen-free, with toluene is solvent, butyleneglycol is an initiator, and to the aliphatics cyclic ester monomer: the stannous octoate that adds monomer total mass 1/100～1/1000 in rac-Lactide or the 6-caprolactone is made catalyzer, under 100～120 ℃ of heating and stirring condition, polymerization time is 12～72h, product precipitation agent sedimentation is filtered, washing, vacuum-drying obtains the aliphatic polyester that two end groups are hydroxyl; Comprise two hydroxy-end capped polylactides and two hydroxy-end capped poly-epsilon-caprolactone;
(2) under the condition of anhydrous and oxygen-free, then under the condition of anhydrous and oxygen-free, the aniline tetramer of two carboxy blockings of mole number and above-mentioned two hydroxy-end capped aliphatic polyester such as getting is dissolved in the N-Methyl pyrrolidone, the dicyclohexylcarbodiimide that the aniline pentamer mole number of the two carboxy blockings of adding is 1～5 times is made condensing agent, under ice-water bath and stirring condition, reaction times is 12～72h, product precipitation agent sedimentation, filter, washing, vacuum-drying obtains (AB) n type segmented copolymer of aniline pentamer of the present invention and aliphatic polyester.
10. a kind of aniline oligomer as claimed in claim 5 and aliphatic polyester the preparation method of many blocks (ABA) n type multipolymer, it is characterized in that step and condition are:
(1) step and the condition of the synthetic method of two hydroxy-end capped aliphatic polyesters:
Under the condition of anhydrous and oxygen-free, with toluene is solvent, butyleneglycol is an initiator, and to the aliphatics cyclic ester monomer: the stannous octoate that adds monomer total mass 1/100～1/1000 in rac-Lactide or the 6-caprolactone is made catalyzer, under 100～120 ℃ of heating and stirring condition, polymerization time is 12～72h, product precipitation agent sedimentation is filtered, washing, vacuum-drying obtains the aliphatic polyester that two end groups are hydroxyl; Comprise two hydroxy-end capped polylactides and two hydroxy-end capped poly-epsilon-caprolactone;
(2) under the condition of anhydrous and oxygen-free, the two hydroxy-end capped aliphatic polyester of getting 2 times of the aniline pentamer of two carboxy blockings and aniline pentamers that mole number is this pair carboxy blocking is dissolved in the N-Methyl pyrrolidone, the dicyclohexylcarbodiimide that adds mole number and be 1～5 times of the aniline pentamer of this pair carboxy blocking is made condensing agent, under ice-water bath and stirring condition, reaction times is 12～72h, product precipitation agent sedimentation, filter, washing, vacuum-drying, again the tertiary butyl is taken off, obtained three block prepolymers of aniline pentamer and aliphatic polyester; Then under the condition of anhydrous and oxygen-free, in three block prepolymers of the described aniline tetramer and aliphatic polyester 1 of mole number such as adding, 6 hexamethylene diisocyanates, the stannous octoate that adds three block prepolymer mole numbers 0.1～1% of aniline pentamer and aliphatic polyester is made catalyzer, under 55～65 ℃ and the agitation condition, reaction times is 6～12h, product precipitation agent sedimentation, filter, washing, vacuum-drying obtains (ABA) n type segmented copolymer of aniline pentamer of the present invention and aliphatic polyester.
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| CN111171301B (en) * | 2020-02-12 | 2021-04-06 | 东华大学 | Preparation method and application of nitrogenous copolymerized polylactic acid |
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