CN1546549A - Bio-degradability polyester block macromolecule copolymer, preparation method and uses - Google Patents
Bio-degradability polyester block macromolecule copolymer, preparation method and uses Download PDFInfo
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Abstract
The invention discloses a bio-degradabble polyester block macromolecule copolymer, preparation method and uses thereof, which has the formula described in the specification, wherein the R1 group of the A block fragment is saturated straight chain alkylidene having 1-6 carbon atoms, unsaturated straight chain alkylidene or alicyclic group, the R2 group is saturated straight chain alkylidene having 2-10 carbon atoms, unsaturated straight chain alkylidene or alicyclic group, the R3 group of the B block fragment is H or CH3, and for the circumstance that R3=CH3, the adjacent carbon atom of the R3 is chirality R or S spatial configuration, the average number molecular weight of the polyester block copolymer is 1,000-300,000, the block molar weight percentage of the A chain fragment is 0-100%, while the block molar weight percentage of the B chain fragment is 100%-0.
Description
Technical field
The present invention relates to a kind of Biodegradable polyester high-molecular block copolymer, preparation method and purposes.The segmented copolymer that this invention provided is an ABA type polyester three-block multipolymer, is a kind of thermoplastically, crystalline completely biodegradable macromolecular material.Its chemical structure characteristic: A chain segment is a ring-type lactides compound monomer, the copolymerization chain segment that obtains through ring-opening polymerization; B chain segment is by aliphatic dibasic acid and derivative and aliphatic dihydroxy alcohol or polyvalent alcohol, the hydroxy functional group end-blocking aliphatic polyester prepolymer for preparing through the condensation polymerization reaction.This biological degradability block macromolecular multipolymer can be used as the functional living being medical material, and medicament slow release is put pharmaceutical adjunct or environment friendly macromolecular material.
Background technology
Synthesize the important organic acid product-lactic acid that obtains based on fermentation process, can prepare high molecular weight polylactic acid (PLA) through further organic and polymer chemistry polymerization process.Poly(lactic acid) is as the important aliphatic poly ester material of a class at present, because its good hydrolysis, enzyme biodegradability, low cytotoxicity and high degree of biocompatibility, particularly its to add water degraded final product be lactic acid, known in life entity ubiquity, therefore absorbed by the intravital bio-metabolic process of life easily, therefore, has huge real world applications prospect in related application fields such as bio-medical material, modern pharmaceutical.On the other hand, high molecular weight polylactic acid has heat physical properties and the processing characteristics close with general engineering plastic polypropylene (PP), and the waste after its product uses, being found can be for excretory vitro enzyme institutes of Institute of Micro-biology such as the extensive bacterium that exists of occurring in nature, fungi thoroughly degrade, moneyization, finally be converted into carbonic acid gas and water, therefore a kind of possible biological degradability equivalent material as current interchangeable heat thermoplastic plastic also has important use value and wide market development prospect.Usually the high molecular polymer of lactic acid has three kinds of different existing waies: poly-(L-lactic acid) PLLA that (1) is made of the optical pure L-lactic acid polymerized unit, and it is the crystallinity polyester macromolecule, fusing point 165～185 degree, second-order transition temperature 50～60 degree; (2) poly-(D-lactic acid) PDLA that is made of optical purity D-lactic acid polymerizes unit is non-crystalline polyester macromolecule; (3) PDLLA that is obtained by the three-dimensional copolymerization of optics racemization or L/D blended lactic acid units is rendered as the material of corresponding amorphous, transparent or low-crystallinity.
At present the main route of synthetic macromolecule amount poly(lactic acid) has: (1) at organometallic compound (as organotin, catalyzer such as organic zinc) under the catalysis, by the activation of lactide monomer and obtained common recognition " coordination insertion " mode at present, ring-opening polymerization prepares high-molecular weight PLA.(2) under the organo-metallic catalyst, by the synthetic preparation of high-pure lactic acid direct polymerization high-molecular weight PLA.In a kind of synthetic method, suppose absolute anhydrous words in the polymerization system before above-mentioned, the compound with active structure of functional groups such as hydroxyl, amino is necessary as the initiator of ring-opening polymerization.Simultaneously, structure design by small molecules or macromole initiator, the PLA that contains biological activity terminal functionality (VITAMIN, steroidal compounds, hormone etc.) can be prepared on the one hand, functional high-polymer segmented copolymer can also be prepared on the other hand with AB or ABA type polymer chain structure.Recently, U.S. Pat 6579951 reports utilize two hydroxy-end capped polyethylene oxides (PEO) to prepare A (BCB) A type segmented copolymer as B segment, poly(propylene oxide) (PPO) for the C segment, and wherein A is optically active polyester segment, as the polylactic acid chain segment.Chinese patent CN1111253A has also reported the ABA type polymer triblock copolymer with similar structures, wherein B is that the polyether glycol segment is (as polyoxyethylene glycol PEG, polytetramethylene glycol PBD), A is the poly(lactic acid) segment, but this three block macromoleculars multipolymer is a kind of biological dissolution sexual function polymer with good mechanical strength and biocompatibility.In addition, Polymer J.2002,34,203 and Polymer 2000,41,7369 have reported the ABA triblock copolymer with similar polymer chain structure based on the lactic acid polymer preparation respectively, and wherein corresponding B segment is respectively PTMC (PTMC), poly-(R, S)-3-butyric ester (PHB).Generally speaking, the random copolymerization of lactic acid and other copolymerization units can only obtain low-crystalline or non-crystalline polymer, the mechanical and physical performance shortcoming, and the result of above bibliographical information shows, method by the block copolymerization modification, can realize main machinery, physics based on poly(lactic acid), processibility and biodegradability, material physical chemistry performance (fusing point finally further is provided, second-order transition temperature, hardness, impact strength, biodegradation rate, forming process temperature etc.) the more wide series of biologic degradation property functional high molecule material of modification scope.
On the other hand, react through Louis acid catalysis condensation polymerization down, can synthesize and prepare another kind of important biological degradability, biocompatibility aliphatic polyester polymer material by aliphatic dibasic acid/dibasic alcohol.U.S. Pat 5310782, Japan fiber association will, 1996,52,320, Polym.Degra.Stab., 1998,59,209 have reported high molecular polyethylene glycol succinate (PES) respectively, poly butylene succinate (PBS), the new synthetic method of poly adipate succinic acid ester (PBA), this wherein PBS obtain via the condensation polymerization prepared in reaction by 4 carbon, two acid compounds Succinic Acid and 4 carbon glycols compound butyleneglycols.High-molecular weight poly butylene succinate (PBS) has the fusing point of 114～118 degree, second-order transition temperature about-40 degree, pyrolytic decomposition temperature about 380 degree, good breaking elongation performance, excellent biological degradability and biocompatibility and the close processing flowability of linear low density polyethylene, thereby as a kind of biodegradable polymer with significant application value that becomes such aliphatic polyester.Nearest European Polymer J., 2002,38,305 have reported binary blend and the application in the aids drug slowly-releasing is put based on biological degradability PBS and PLLA, but the uncompatibility of this polymer binary blends makes that the material property of final preparation is unsatisfactory.
For above-mentioned polymeric fatty adoption ester via the polycondensation process preparation, existing experimental result shows the control by reactant feed ratio and polymerization process, can realize that preparation has end capped aliphatic polyester prepolymer of hydroxy functional group and macromole.By the set out formulating of recipe of dibasic alcohol in the raw material or polyol structure of polymerization, can also synthesize preparation and have height cladodification or " starlike " molecular structure and hydroxy-end capped two dimension or three-dimensional aliphatic polyester compound simultaneously.The active terminal hydroxy group functional group that above Biodegradable polyester prepolymer or macromole are entrained, can be used as macromole function initiator (initiator), under the effect of catalyzer such as organometallic reagent, with active lactide or cyclic lactone class monomer reaction, controlled copolymerization prepares functional diblock or three block biological degradability multipolymers.
Synthesize the aliphatic poly ester large molecule initiator (initiator) that prepared in reaction obtains based on polycondensation with hydroxy functional group closed-end structure, by further with lactide analog monomer (glycollide, rac-Lactide) block copolymerization, can prepare Biodegradable polyester multipolymer with novel macromolecule structure, for example by two hydroxy-terminated polyester B segment macromole initiators and rac-Lactide and organo-metallic catalyst reaction, the triblock copolymer PLA-b-B-b-PLA that can prepare, reach the second-order transition temperature that reduces PLA, improve the tension set of PLA and the Physical Processing performance of regulating material, the purpose of biological degradability speed is therefore at bio-medical material, the pharmaceutical industry of medicine controllable sustained-release, fields such as environment-friendly material have a good application prospect.
Content of the present invention
The biological degradability poly(lactic acid) is crisp, second-order transition temperature is high in order to solve in the present invention, the difficult adjusting of biodegradation rate, even by with the general random copolymerization of second constituent monomers, its product exists also that the molecular chain regularity is poor, crystallinity is low, and mechanical strength is not as problems such as people's wills.
The present invention seeks to provide a kind of Biodegradable polyester block macromolecular multipolymer with novel molecular chain structure.
Another purpose of the present invention provides a kind of Biodegradable polyester block macromolecular copolymer method of above-mentioned novel molecular chain structure.
Purpose of the present invention also provides a kind of purposes of Biodegradable polyester block macromolecular multipolymer of above-mentioned novel molecular chain structure.
The Biodegradable polyester block macromolecular multipolymer of new A BA shape molecular chain structure provided by the present invention has following chemical structure of general formula:
Compound 1
In the macromolecular structure of above-mentioned segmented copolymer 1, B chain segment R
1Group is the saturated straight chain alkylidene group of carbonatoms 0～8, unsaturated straight-chain alkyl-sub-or alicyclic group; R
2Group is the saturated straight chain alkylidene group of carbonatoms 2～10, unsaturated straight-chain alkyl-sub-or alicyclic group, perhaps CH
2-CHR
4-CH
2, CH
2-CHR
4-CHR
4-CH
2, CH
2-CHR
4-CHR
4-CHR
4-CH
2, CH
2-CHR
4-CHR
4-CHR
4-CHR
4-CH
2Group, above-mentioned R
2R in the group
4Be the possible polymer side chain based on polyvalent alcohol, its chemical structure of general formula is as follows:
R
4Chemical structure
Above-mentioned R
4In the chemical structure of polymer side chain, R
5Group is the saturated straight chain alkylidene group of carbonatoms 0～8, unsaturated straight-chain alkyl-sub-or alicyclic group, R
6Group is the saturated straight chain alkylidene group of carbonatoms 2～10, unsaturated straight-chain alkyl-sub-or alicyclic group, and the mean polymerisation degree Z of polymer side chain is 0～100 simultaneously.
In the macromolecular structure of above-mentioned block polyester high-molecular copolymer 1, A chain segment R
3Group can be H, CH
3, and at R
3=CH
3Situation under, R
3Adjacent carbons can be chirality R or S steric configuration.The number average molecular weight of above-mentioned polyester ABA segmented copolymer is 1,000～300,000, and the pulsating molecular fraction X of A chain can be 0～100% in its polymer chemistry structure, and the pulsating molecular fraction 2Y of B chain can be for being 100%～0.In other words, Biodegradable polyester polymer provided by the present invention can be
Perhaps
Homopolymer, also can be both segmented copolymers.
A kind of preparation method with Biodegradable polyester segmented copolymer of novel molecular chain structure provided by the present invention is mainly constituted the preparation feature by two stage successive reactions.It is the initial synthetic raw material that sets out that fs reaction is based on diprotic acid and derivative thereof and dibasic alcohol and polyvalent alcohol, via the end capped aliphatic polyester prepolymer of condensation polymerization prepared in reaction hydroxy functional group.Subordinate phase reaction is to be B chain segment with the polyester prepolyer that previous step prepares, under catalyst action, further with the synthetic preparation of lactide monomers copolymerization high-molecular weight Biodegradable polyester segmented copolymer.
Compound 2
According to a kind of preparation method with Biodegradable polyester ABA shape segmented copolymer of novel molecular chain structure provided by the present invention, the end capped B chain of hydroxy functional group segment (compound 2) is via the synthetic preparation of condensation polymerization reaction aliphatic polyester prepolymer.The number-average molecular weight of above-mentioned polyester prepolyer can be 1,000～50,000, and more satisfactory number-average molecular weight is 1,000～35,000, preferably 1,000～20,000.
In above-mentioned polyester prepolyer compound 2 chemical structures, R
1Group is the saturated straight chain alkylidene group of carbonatoms 0～8, unsaturated straight-chain alkyl-sub-or alicyclic group; R
2Group is the saturated straight chain alkylidene group of carbonatoms 2～10, unsaturated straight-chain alkyl-sub-or alicyclic group, perhaps CH
2-CHR
4-CH
2, CH
2-CHR
4-CHR
4-CH
2, CH
2-CHR
4-CHR
4-CHR
4-CH
2, CH
2-CHR
4-CHR
4-CHR
4-CHR
4-CH
2Group, above-mentioned R
2R in the group
4Be possible polymer side chain based on polyvalent alcohol.At possible R
4In the chemical structure of polymer side chain, R
5Group is the saturated straight chain alkylidene group of carbonatoms 0～8, unsaturated straight-chain alkyl-sub-or alicyclic group, R
6Group is the saturated straight chain alkylidene group of carbonatoms 2～10, unsaturated straight-chain alkyl-sub-or alicyclic group, and the mean polymerisation degree Z of polymer side chain is 0～100 simultaneously.
According to a kind of preparation method provided by the present invention with Biodegradable polyester ABA block polymer of novel molecular chain structure, the unit molecule hydroxy functionality of its polyester prepolyer compound 2 can be 2～10, more satisfactory is 2～8, is preferably 2～6.
Synthetic one of raw material compound 3 that sets out of the end capped aliphatic polyester prepolymer of above-mentioned hydroxy functional group (compound 2), in the above-mentioned chemical structure of general formula, R
1Group is the saturated straight chain alkylidene group of carbonatoms 0～8, unsaturated straight-chain alkyl-sub-or alicyclic group.R
7Be hydrogen, low alkyl group, aromatic substituent, the possible carbonatoms 1～6 of low alkyl group wherein, preferably carbonatoms is 1～4 alkyl, and the possible carbonatoms of aromatic substituent is 6～10, and more satisfactory is that carbonatoms is 6～8.The general compound 3 that is adopted has oxalic acid, dialkyl oxalate, propanedioic acid, dialkyl malonate, succsinic acid, Succinic acid dimethylester, ethyl succinate, diisopropyl ester, dibutylester, diphenyl ester, pentanedioic acid, pentanedioic acid dialkyl, hexanodioic acid, hexanodioic acid dialkyl, suberic acid, certain herbaceous plants with big flowers diacid etc.According to the condensation polymerization of polyester prepolyer compound 2 and as the real reaction effect of macromole initiator, more satisfactory R in the above-mentioned possible reactant
1Group is the alkylidene group of carbonatoms 0～8, it would be desirable that carbonatoms is 0～6 alkylidene group.
According to a kind of preparation method provided by the present invention, two compounds 4 of the synthetic raw material that sets out of aliphatic polyester prepolymer (compound 2), R in its chemical structure of general formula with Biodegradable polyester ABA shape segmented copolymer of novel molecular chain structure
8Group is the saturated straight chain alkylidene group of carbonatoms 2～10, unsaturated straight-chain alkyl-sub-or alicyclic group, perhaps polyhydric CH
2-CH (OH)-CH
2, CH
2-CH (OH)-CH (OH)-CH
2, CH
2-CH (OH)-CH (OH)-CH (OH)-CH
2, CH
2-CH (OH)-CH (OH)-CH (OH)-CH (OH)-CH
2Such as according to preparation method provided by the present invention, possible compound 4 is an ethylene glycol, 1, ammediol, 1,3 butylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,10-certain herbaceous plants with big flowers glycol, 1,4-cyclohexane diol, glycerine, tetrahydroxybutane, Xylitol, sorbyl alcohol etc.
HO-R
8-OH
4
According to a kind of preparation method provided by the present invention with Biodegradable polyester ABA shape segmented copolymer of novel molecular chain structure, feeding intake as two compound 4 of the synthetic raw material that sets out of aliphatic polyester prepolymer (compound 2) is can a kind of this compounds, also can be two kinds or two or more mixtures of dibasic alcohol and polyvalent alcohol, wherein the possible molar ratio range of dibasic alcohol and polyvalent alcohol be 0～100%.
Synthesizing of above-mentioned polyester prepolyer compound 2: (1) synthesis under normal pressure stage, (2) negative reaction stage via two stages.The temperature range that synthesis under normal pressure stage transesterification reaction is possible is 120～300 ℃, and relatively the ideal polymeric reaction temperature is 120～300 ℃, and best is 180～250 ℃.Small molecule by-product is removed in the polycondensation of carrying out under the negative pressure, and possible temperature range is 150～300 ℃, and relatively ideal condensation polymerization temperature is 180～270 ℃, and optimal is 180～240 ℃.
The synthetic starting material that set out of above-mentioned polyester prepolyer 2 can be a kind of compound 3 and a kind of compound 4 or multiple compound 4, and in other words, this polyester prepolyer compound 2 can be that aliphatics polycondensation ester also can be aliphatic mixed polycondensation ester.
It is 1～5 * 10 that possible vacuum ranges is implemented in the condensation polymerization reaction in above-mentioned negative pressure stage
4Pa, relatively the ideal vacuum ranges is 1～2.5 * 10
4Pa, best is 1～1.5 * 10
4Pa.
It is metal, organo-tin compound, organo-aluminium compound, organic germanium compounds, organic titanic compound, organoiron compound etc. that above-mentioned polyester prepolyer compound 2 synthetic transesterifys and condensation polymerization stage are adopted possible catalyzer, for example sulfonic acid, tosic acid, glass putty, tin tetrachloride, tindichloride, tin alkyl, aluminum alkyls, alkyl titanium, zinc alkyl(s), aluminum alkoxide, titan-alkoxide, stannic acid ester, alkoxyl group germanium, iron lactate etc.Simultaneously also can not adopt catalyzer.
Above-mentioned polyester prepolyer compound 2 synthetic employings in the raw material that sets out, the possible scope of design mol ratio of compound 4 hydroxy functional groups and compound 3 carbonyl groups of feeding intake is 1～3.0, more satisfactory molar ratio range be 1～2.0, optimal molar ratio range is 1～1.8.
According to a kind of preparation method provided by the present invention with biological degradability ABA shape polyester block copolymer of novel molecular chain structure, above-mentioned two kinds of set out starting compound 3 and 4 esterifications and condensation polymerization reactions, under the situation that adopts catalyzer, during with respect to 1 mole of the total amount that contains carbonyl compound 3 in the reaction raw materials, possible catalyzer usage quantity scope is 10
-6～10 moles, more satisfactory is 10
-5～1 mole, it would be desirable 10
-4～1 mole.
Above-mentioned polyester prepolyer 2 is a white solid, and according to the preparation method that this invention provided, the thick product of resultant can be purified by the sedimentary method of good solvent/poor solvent.For example will generate compound 2 earlier and be dissolved in the chloroform, and add excessive methanol solution precipitation, and it would be desirable that aforesaid operations will repeat 3～5 times, last throw out passes through vacuum-drying and purifying.
According to a kind of preparation method with Biodegradable polyester ABA shape segmented copolymer of novel molecular chain structure provided by the present invention, A chain segment is to synthesize preparation as macromole initiator, ring-type lactide monomers and catalyzer via the second step ring-opening copolymerization by the end capped polyester prepolyer compound 2 of hydroxy functional group.
Above-mentioned possible lactides ring-type macromonomer is glycollide, rac-Lactide.Under the situation of rac-Lactide, can be optically active (R, R) or (S, S) type rac-Lactide also can be (R, S) rac-Lactide of meso or racemic form.
The reaction of above-mentioned ring-opening copolymerization can be implemented by the method for fusion mass polymerization or solution polymerization, under the situation of solution copolymerization, possible solvent has benzene,toluene,xylene, phenyl ether, dioxane etc., and more satisfactory have toluene, dimethylbenzene.
It is 60～250 degree that possible temperature range is implemented in above-mentioned ring-opening copolymerization reaction, and more satisfactory temperature range is 80～220 degree, and best temperature range is 80～150 degree.
The catalyzer that above-mentioned ring-opening copolymerization reaction may be adopted is metal, organo-tin compound, organo-aluminium compound, organic germanium compounds, organic titanic compound, organoiron compound etc., for example sulfonic acid, tosic acid, glass putty, tin tetrachloride, tindichloride, tin alkyl, aluminum alkyls, alkyl titanium, zinc powder, zinc alkyl(s), aluminum alkoxide, titan-alkoxide, stannic acid ester, alkoxyl group germanium, iron lactate etc.
Above-mentioned ring-opening copolymerization catalyst for reaction, hydroxy functional group mole number with the macromole initiator is under the situation of 1 benchmark, the possible mole number scope of catalyzer is 0.00001～5, and more satisfactory mole number scope is 0.0001～5, and best catalyst levels scope is 0.001～2.
According to a kind of preparation method provided by the present invention with Biodegradable polyester ABA shape segmented copolymer of novel molecular chain structure, implement the ring-opening copolymerization reaction process by the pulsating the first step reaction of B and second step, obtain final product of the present invention.Outward appearance is the compound of white crystalline or low-crystalline.Final product is by the passable further purification of demand, its possible purification process is: earlier final product is dissolved in its good solvent, as methylene dichloride, in the trichloromethane, after removing by filter not capacitive impurity, pour excessive cold poor solvent into,, filter vacuum-drying to constant weight as precipitations such as methyl alcohol, ethanol, normal hexane, normal heptanes.
A kind of purposes with Biodegradable polyester ABA shape segmented copolymer of novel molecular chain structure provided by the present invention mainly is the auxiliary biomaterial of bio-medical material, drug controllable release preparation, environment-friendly material.
Description of drawings
Accompanying drawing 1 is the carbon-13 magnetic resonance spectrogram of embodiment 9 according to the prepared Biodegradable polyester segmented copolymer of method of the present invention.
Accompanying drawing 2 is according to the prepared Biodegradable polyester segmented copolymer of method provided by the invention and with reference to the wide-angle x-ray diffraction collection of illustrative plates of corresponding homopolymer.
In the accompanying drawing: Chemical shift (ppm)-chemical shift, 2 θ Diffraction Angle-diffraction angle.
It is local in the accompanying drawing 1 that what amplify is carbonyl functional group's NMR signal, a wherein, and b represents respectively is carbon-13 magnetic resonance signal from succinyl-and lactoyl polymerized unit carbonyl.Generally under the random copolymerization situation, because the influence that segment distributes with statistical law, a also can occur between the b signal because the carbonyl sub signal that sequence distributes and produced, but accompanying drawing 1 can only be observed the carbonyl signal of corresponding homopolymer, illustrates that this multipolymer is a polyester block copolymer.
Code in the accompanying drawing 2: H14, H12, H23, H11, H32, H21, H31 correspond respectively to embodiment 4,5,6,7,8,9,10 synthetic prepared block copolymerization matter samples, the result can find that sample H12, H23, H11, H32, H21, H31 exist PLLA and two kinds of crystal habits of PBS simultaneously, illustrate that according to the prepared multipolymer of the inventive method be polyester block copolymer from figure
Advantage of the present invention
There are following advantage in a kind of biological degradability block macromolecular copolymer provided by the present invention, preparation method and purposes:
(1) whole synthetic preparation process is simple, implements easily.
(2) according to the preparation method of a kind of biological degradability block macromolecular copolymer provided by the present invention, synthesize Sending out main raw material(s) is biocompatibility native compound and derivative thereof, can be by the highly efficient regeneration natural resources Chemistry or biotransformation obtain, and utilization of resources potentiality are big, have to drive relevant synthetic upstream chemical substance The advantage of industrial chain.
(3) according to the synthetic preparation of the preparation method of a kind of biological degradability block macromolecular copolymer provided by the present invention The ABA shape macromolecule that obtains, the importing of B chain segment not only can reduce and synthesize into respect to the PLA homopolymers This regulates product crystallinity, thermophysical property, biodegradation rate, and can regulate the product processing characteristics.
(4) the prepared biological degradability block macromolecular copolymer of method that provides according to this invention is by the B chain The adjusting of segment and A chain fragment length can realize oneself of the performances such as product machinery, physics, processing, biological degradability By adjusting.
(5) the prepared biological degradability block macromolecular copolymer of method that provides according to this invention, its biodegradation Product is nontoxic or hypotoxic chemical substance, relatively is suitable as bio-medical material, medicine controlled release system Agent assists biomaterial, environment-friendly material to use.
Embodiment
By the following examples the present invention is specifically described, will helps to understand the present invention, but do not limit content of the present invention.
Chemical analysis method that is adopted among the embodiment and analytical instrument specify as follows:
[molecular weight and molecular weight distribution]
Molecular weight and molecular weight distribution according to the resulting a kind of biological degradability block macromolecular multipolymer of preparation method provided by the present invention are measured by gel permeation chromatography (GPC, Waters company) instrument.The polystyrene of serial molecular weight with narrow molecular weight distributions is as proofreading and correct standard specimen, and trichloromethane is as the drip washing phase, and measuring temperature is 40 ℃.
[chemical constitution and structure]
Structure according to preparation method's gained compound provided by the present invention is passed through solution nucleus magnetic resonance and infrared spectroscopic determination with composition, and the mensuration temperature of nucleus magnetic resonance is a room temperature, and solvent is a trichloromethane.
[heat physical properties]
By differential scanning calorimetry method (DSC), the fusing point of compound and second-order transition temperature can record.And by thermogravimetry (TGA), the heat decomposition temperature of gained compound also can be measured and obtain.
[crystal property]
Crystal property according to preparation method's gained compound provided by the present invention can be measured by the wide-angle x-ray diffraction method.Measure the temperature room temperature, incident wavelength 0.154nm.
Embodiment 1
Earlier with 59.0g succsinic acid and 54.0g 1, the 4-butyleneglycol joins in the 500mL volume three neck round-bottomed flasks that high pure nitrogen replaced successively under the room temperature.There-necked flask is equipped high purity nitrogen inlet mouth, mechanical stirrer, condensation water trap simultaneously.Above-mentioned reaction system is moved in the oil bath of 210 degree, logical nitrogen stirring reaction is after 4 hours, and slowly decompression was reacted 4 hours again, and the final vacuum tightness of above-mentioned reaction system is 0.5mmHg.After the product cooling of above-mentioned polyreaction, be dissolved in trichloromethane earlier, filter then, add excessive cold methanol in the gained filtrate.Obtain the polyester prepolyer product through separation, drying.Heat content 93.2J/g, heat decomposition temperature 402.2 degree are spent, melted to its number-average molecular weight 4.9KDa (nuclear magnetic resonance method), 6.8KDa (GPC method), molecular weight distribution coefficient 2.34, fusing point 115.1.
Embodiment 2
Earlier with 59.0g succsinic acid and 54.0g 1, the 4-butyleneglycol joins in the 500mL volume three neck round-bottomed flasks that high pure nitrogen replaced successively under the room temperature.There-necked flask is equipped high purity nitrogen inlet mouth, mechanical stirrer, condensation water trap simultaneously.Above-mentioned reaction system is moved in the oil bath of 210 degree, logical nitrogen stirring reaction is after 4 hours, and slowly decompression was reacted 0.5 hour again, and the final vacuum tightness of above-mentioned reaction system is 0.5mmHg.After the product cooling of above-mentioned polyreaction, be dissolved in trichloromethane earlier, filter then, add excessive cold methanol in the gained filtrate.Obtain the polyester prepolyer product through separation, drying.Its number-average molecular weight 4.3KDa (GPC method), molecular weight distribution coefficient 2.23.
Embodiment 3
Earlier with 59.0g succsinic acid and 54.0g 1, the 4-butyleneglycol joins in the 500mL volume three neck round-bottomed flasks that high pure nitrogen replaced successively under the room temperature.There-necked flask is equipped high purity nitrogen inlet mouth, mechanical stirrer, condensation water trap simultaneously.Above-mentioned reaction system is moved in the oil bath of 210 degree, logical nitrogen stirring reaction is after 4 hours, and slowly decompression was reacted 1.0 hours again, and the final vacuum tightness of above-mentioned reaction system is 0.5mmHg.After the product cooling of above-mentioned polyreaction, be dissolved in trichloromethane earlier, filter then, add excessive cold methanol in the gained filtrate.Obtain the polyester prepolyer product through separation, drying.Its number-average molecular weight 7.6KDa (GPC method), molecular weight distribution coefficient 2.07.
Comparative example 1
Earlier with 59.0g succsinic acid and 54.0g 1, the 4-butyleneglycol joins in the 500mL volume three neck round-bottomed flasks that high pure nitrogen replaced successively under the room temperature.There-necked flask is equipped high purity nitrogen inlet mouth, mechanical stirrer, condensation water trap simultaneously.Above-mentioned reaction system is moved in the oil bath of 210 degree, logical nitrogen stirring reaction is after 4 hours, and slowly decompression was reacted 3.0 hours again, and the final vacuum tightness of above-mentioned reaction system is 0.5mmHg.After the product cooling of above-mentioned polyreaction, be dissolved in trichloromethane earlier, filter then, add excessive cold methanol in the gained filtrate.Obtain the polyester prepolyer product through separation, drying.Its number-average molecular weight 8.7KDa (GPC method), molecular weight distribution coefficient 2.10.
Embodiment 4
Order adds the stannous octoate toluene solution of 2.0g embodiment 1 gained polyester prepolymer product, 69 microlitres in the 50mL there-necked flask of a process flame drying treatment, and its concentration is 130.0mg/mL, magnetic stick and 0.41g (L, L) rac-Lactide.Above-mentioned reaction system is connected to is heated to 50 degree on the vacuum line and stirs and keep 1.0 hours to remove solvent toluene and residual moisture.Then vacuum line is closed, charge into high pure nitrogen.Above-mentioned reaction system is heated to 120 degree, continued stirring reaction 24.0 hours.The transformation efficiency that records rac-Lactide is 44% (nuclear magnetic resonance method).After the product cooling of above-mentioned polyreaction, be dissolved in trichloromethane earlier, filter then, add excessive cold methanol in the gained filtrate.Obtain polyester block copolymer through separation, drying.In its number-average molecular weight 5.3KDa (nuclear magnetic resonance method), 7.8KDa (GPC method), molecular weight distribution coefficient 2.05, the prepared ABA segmented copolymer, A segment lactic acid polymerizes unit (O-CH (CH
3)-COO-CH (CH
3The mol ratio of)-CO-) and B segment butylene succinate polymerized unit is 0.11: 1 (nuclear magnetic resonance method), fusing point 110.8 degree (B segment), melts heat content 87.9J/g (B segment), heat decomposition temperature 232.0 degree (A segment), heat decomposition temperature 375.6 degree (B segment).
Embodiment 5
Order adds the stannous octoate toluene solution of 2.0g embodiment 1 gained polyester prepolymer product, 69 microlitres in the 50mL there-necked flask of a process flame drying treatment, and its concentration is 130.0mg/mL, magnetic stick and 0.83g (L, L) rac-Lactide.Above-mentioned reaction system is connected to is heated to 50 degree on the vacuum line and stirs and keep 1.0 hours to remove solvent toluene and residual moisture.Then vacuum line is closed, charge into high pure nitrogen.Above-mentioned reaction system is heated to 120 degree, continued stirring reaction 24.0 hours.The transformation efficiency that records rac-Lactide is 62% (nuclear magnetic resonance method).After the product cooling of above-mentioned polyreaction, be dissolved in trichloromethane earlier, filter then, add excessive cold methanol in the gained filtrate.Obtain polyester block copolymer through separation, drying.In its number-average molecular weight 6.2KDa (nuclear magnetic resonance method), 9.0KDa (GPC method), molecular weight distribution coefficient 2.09, the prepared ABA segmented copolymer, A segment lactic acid polymerizes unit (O-CH (CH
3)-COO-CH (CH
3)-CO-) and B segment butylene succinate polymerized unit (CO-CH
2-CH
2-COO-CH
2-CH
2-CH
2-CH
2-O-) mol ratio is 0.31: 1 (nuclear magnetic resonance method), fusing point 110.0 degree (B segment), melts heat content 74.3J/g (B segment), heat decomposition temperature 237.0 degree (A segment), heat decomposition temperature 376.6 degree (B segment).
Embodiment 6
Order adds the stannous octoate toluene solution of 2.0g embodiment 1 gained polyester prepolymer product, 69 microlitres in the 50mL there-necked flask of a process flame drying treatment, and its concentration is 130.0mg/mL, magnetic stick and 1.10g (L, L) rac-Lactide.Above-mentioned reaction system is connected to is heated to 50 degree on the vacuum line and stirs and keep 1.0 hours to remove solvent toluene and residual moisture.Then vacuum line is closed, charge into high pure nitrogen.Above-mentioned reaction system is heated to 120 degree, continued stirring reaction 24.0 hours.The transformation efficiency that records rac-Lactide is 81% (nuclear magnetic resonance method).After the product cooling of above-mentioned polyreaction, be dissolved in trichloromethane earlier, filter then, add excessive cold methanol in the gained filtrate.Obtain polyester block copolymer through separation, drying.In its number-average molecular weight 7.1KDa (nuclear magnetic resonance method), 9.9KDa (GPC method), molecular weight distribution coefficient 2.12, the prepared ABA segmented copolymer, A segment lactic acid polymerizes unit (O-CH (CH
3)-COO-CH (CH
3)-CO-) and B segment butylene succinate polymerized unit (CO-CH
2-CH
2-COO-CH
2-CH
2-CH
2-CH
2-O-) mol ratio is 0.54: 1 (nuclear magnetic resonance method), fusing point 150.1 degree (A segment), melt heat content 8.55J/g (A segment), fusing point 109.2 degree (B segment), melt heat content 62.5J/g (B segment), heat decomposition temperature 250.5 degree (A segment), heat decomposition temperature 380.6 degree (B segment).
Embodiment 7
Order adds the stannous octoate toluene solution of 2.0g embodiment 1 gained polyester prepolymer product, 69 microlitres in the 50mL there-necked flask of a process flame drying treatment, and its concentration is 130.0mg/mL, magnetic stick and 1.65g (L, L) rac-Lactide.Above-mentioned reaction system is connected to is heated to 50 degree on the vacuum line and stirs and keep 1.0 hours to remove solvent toluene and residual moisture.Then vacuum line is closed, charge into high pure nitrogen.Above-mentioned reaction system is heated to 120 degree, continued stirring reaction 24.0 hours.The transformation efficiency that records rac-Lactide is 82% (nuclear magnetic resonance method).After the product cooling of above-mentioned polyreaction, be dissolved in trichloromethane earlier, filter then, add excessive cold methanol in the gained filtrate.Obtain polyester block copolymer through separation, drying.In its number-average molecular weight 8.3KDa (nuclear magnetic resonance method), 10.2KDa (GPC method), molecular weight distribution coefficient 2.22, the prepared ABA segmented copolymer, A segment lactic acid polymerizes unit (O-CH (CH
3)-COO-CH (CH
3)-CO-) and B segment butylene succinate polymerized unit (CO-CH
2-CH
2-COO-CH
2-CH
2-CH
2-CH
2-O-) mol ratio is 0.82: 1 (nuclear magnetic resonance method), fusing point 156.5 degree (A segment), melt heat content 25.6J/g (A segment), fusing point 108.4 degree (B segment), melt heat content 49.5J/g (B segment), heat decomposition temperature 254.8 degree (A segment), heat decomposition temperature 371.6 degree (B segment).
Embodiment 8
Order adds the stannous octoate toluene solution of 2.0g embodiment 1 gained polyester prepolymer product, 69 microlitres in the 50mL there-necked flask of a process flame drying treatment, and its concentration is 130.0mg/mL, magnetic stick and 2.48g (L, L) rac-Lactide.Above-mentioned reaction system is connected to is heated to 50 degree on the vacuum line and stirs and keep 1.0 hours to remove solvent toluene and residual moisture.Then vacuum line is closed, charge into high pure nitrogen.Above-mentioned reaction system is heated to 120 degree, continued stirring reaction 24.0 hours.The transformation efficiency that records rac-Lactide is 87% (nuclear magnetic resonance method).After the product cooling of above-mentioned polyreaction, be dissolved in trichloromethane earlier, filter then, add excessive cold methanol in the gained filtrate.Obtain polyester block copolymer through separation, drying.In its number-average molecular weight 10.2KDa (nuclear magnetic resonance method), 11.1KDa (GPC method), molecular weight distribution coefficient 2.18, the prepared ABA segmented copolymer, A segment lactic acid polymerizes unit (O-CH (CH
3)-COO-CH (CH
3)-CO-) and B segment butylene succinate polymerized unit (CO-CH
2-CH
2-COO-CH
2-CH
2-CH
2-CH
2-O-) mol ratio is 1.31: 1 (nuclear magnetic resonance method), fusing point 157.0 degree (A segment), melt heat content 35.2J/g (A segment), fusing point 108.1 degree (B segment), melt heat content 36.2J/g (B segment), heat decomposition temperature 267.2 degree (A segment), heat decomposition temperature 381.9 degree (B segment).
Embodiment 9
Order adds the stannous octoate toluene solution of 2.0g embodiment 1 gained polyester prepolymer product, 69 microlitres in the 50mL there-necked flask of a process flame drying treatment, and its concentration is 130.0mg/mL, magnetic stick and 3.30g (L, L) rac-Lactide.Above-mentioned reaction system is connected to is heated to 50 degree on the vacuum line and stirs and keep 1.O hour to remove solvent toluene and residual moisture.Then vacuum line is closed, charge into high pure nitrogen.Above-mentioned reaction system is heated to 120 degree, continued stirring reaction 24.0 hours.The transformation efficiency that records rac-Lactide is 87% (nuclear magnetic resonance method).After the product cooling of above-mentioned polyreaction, be dissolved in trichloromethane earlier, filter then, add excessive cold methanol in the gained filtrate.Obtain polyester block copolymer through separation, drying.In its number-average molecular weight 12.0KDa (nuclear magnetic resonance method), 12.6KDa (GPC method), molecular weight distribution coefficient 2.21, the prepared ABA segmented copolymer, A segment lactic acid polymerizes unit (O-CH (CH
3)-COO-CH (CH
3)-CO-) and B segment butylene succinate polymerized unit (CO-CH
2-CH
2-COO-CH
2-CH
2-CH
2-CH
2-O-) mol ratio is 1.74: 1 (nuclear magnetic resonance method), fusing point 162.4 degree (A segment), melt heat content 37.7J/g (A segment), fusing point 106.6 degree (B segment), melt heat content 28.2J/g (B segment), heat decomposition temperature 280.3 degree (A segment), heat decomposition temperature 381.5 degree (B segment).
Embodiment 10
Order adds the stannous octoate toluene solution of 2.0g embodiment 1 gained polyester prepolymer product, 69 microlitres in the 50mL there-necked flask of a process flame drying treatment, and its concentration is 130.0mg/mL, magnetic stick and 3.30g (L, L) rac-Lactide.Above-mentioned reaction system is connected to is heated to 50 degree on the vacuum line and stirs and keep 1.0 hours to remove solvent toluene and residual moisture.Then vacuum line is closed, charge into high pure nitrogen.Above-mentioned reaction system is heated to 120 degree, continued stirring reaction 24.0 hours.The transformation efficiency that records rac-Lactide is 88% (nuclear magnetic resonance method).After the product cooling of above-mentioned polyreaction, be dissolved in trichloromethane earlier, filter then, add excessive cold methanol in the gained filtrate.Obtain polyester block copolymer through separation, drying.In its number-average molecular weight 15.8KDa (nuclear magnetic resonance method), 14.3KDa (GPC method), molecular weight distribution coefficient 2.32, the prepared ABA segmented copolymer, A segment lactic acid polymerizes unit (O-CH (CH
3)-COO-CH (CH
3)-CO-) and B segment butylene succinate polymerized unit (CO-CH
2-CH
2-COO-CH
2-CH
2-CH
2-CH
2-O-) mol ratio is 2.65: 1 (nuclear magnetic resonance method), fusing point 163.5 degree (A segment), melt heat content 45.2J/g (A segment), fusing point 105.6 degree (B segment), melt heat content 19.2J/g (B segment), heat decomposition temperature 291.9 degree (A segment), heat decomposition temperature 367.1 degree (B segment).
Claims (8)
1, a kind of ABA type Biodegradable polyester segmented copolymer, it has following chemical structure of general formula:
In the macromolecular structure of above-mentioned block macromolecular multipolymer, B chain segment R
1Group is the saturated straight chain alkylidene group of carbonatoms 0～8, unsaturated straight-chain alkyl-sub-or alicyclic group; R
2Group is the saturated straight chain alkylidene group of carbonatoms 2～10, unsaturated straight-chain alkyl-sub-or alicyclic group, perhaps CH
2-CHR
4-CH
2, CH
2-CHR
4-CHR
4-CH
2, CH
2-CHR
4-CHR
4-CHR
4-CH
2Or CH
2-CHR
4-CHR
4-CHR
4-CHR
4-CH
2Group; Above-mentioned R
2R in the group
4Be the polymer side chain based on polyvalent alcohol, its chemical structure of general formula is as follows:
R wherein
5Group is the saturated straight chain alkylidene group of carbonatoms 0～8, unsaturated straight-chain alkyl-sub-or alicyclic group, R
6Group is the saturated straight chain alkylidene group of carbonatoms 2～10, unsaturated straight-chain alkyl-sub-or alicyclic group, and the mean polymerisation degree Z of polymer side chain is 0～100 simultaneously; In the macromolecular structure of above-mentioned block polyester high-molecular copolymer, A chain segment R
3Group can be H, CH
3, and at R
3=CH
3Situation under, R
3Adjacent carbons can be chirality R or S steric configuration, the number average molecular weight of above-mentioned polyester ABA segmented copolymer is 1,000～300,000, the pulsating molecular fraction X of A chain can be 0～100% in its polymer chemistry structure, and the pulsating molecular fraction 2Y of B chain can be for being 100%～0.
2, a kind of Biodegradable polyester block macromolecular multipolymer as claimed in claim 1 is characterized in that its number average molecular weight is 1,000～300,000.
3, the pulsating polyester prepolyer of B chain in a kind of Biodegradable polyester segmented copolymer as claimed in claim 1 is characterized in that it has following chemical structure:
Homopolymer, R wherein
1, R
2According to claim 1.
4, a kind of Biodegradable polyester segmented copolymer as claimed in claim 3 is characterized in that its number-average molecular weight is 1,000～50,000.
5, the preparation method of a kind of Biodegradable polyester segmented copolymer as claimed in claim 1 is characterized in that adopting following method to make respectively:
(1), in the presence of catalyzer and normal pressure to 1～5 * 10
4Under the pa negative pressure, 120～300 ℃, molecular formula is HO-R
8The hydroxy functional group of the compound of-OH and molecular formula are
The mol ratio of compound carbonyl group be 1～3.0, reacted 0.5～8 hour, wherein
With the mol ratio of catalyzer be 1: 10
-6～10 moles.R wherein
1According to claim 1, R
7For hydrogen, carbonatoms 1～6 low alkyl group, carbonatoms are 6～10 aromatic substituent, R
8Group is the saturated straight chain alkylidene group of carbonatoms 2～10, unsaturated straight-chain alkyl-sub-or alicyclic group, perhaps polyhydric CH
2-CH (OH)-CH
2, CH
2-CH (OH)-CH (OH)-CH
2, CH
2-CH (OH)-CH (OH)-CH (OH)-CH
2Or CH
2-CH (OH)-CH (OH)-CH (OH)-CH (OH)-CH
2
(2) with fusion mass polymerization or solution polymerization process, method (1) compound that obtains, reacted 1～72 hour under 60～200 ℃ as macromole initiator, ring-type lactide monomers and catalyzer, and their mol ratio was respectively 1: 10
-5～5, wherein the ring-type lactide monomers is glycollide or rac-Lactide;
Described catalyzer is to comprise sulfonic acid, tosic acid, glass putty, tin tetrachloride, tindichloride, tin alkyl, aluminum alkyls, alkyl titanium, zinc powder, zinc alkyl(s), aluminum alkoxide, titan-alkoxide, stannic acid ester, alkoxyl group germanium, the organic sulfonic acid of lactic acid Asia, metal, organo-tin compound, organo-aluminium compound, organic germanium compounds, organic titanic compound, organoiron compound.
6, the preparation method of a kind of Biodegradable polyester segmented copolymer as claimed in claim 5 is characterized in that in the method (2), described rac-Lactide is optically active (R, R) or (S, S) type rac-Lactide, perhaps (R, S) rac-Lactide of meso or racemic form.
7, the preparation method of a kind of Biodegradable polyester segmented copolymer as claimed in claim 5 is characterized in that in the method (2), described solution polymerization process, the solvent of employing are benzene,toluene,xylene, phenyl ether, dioxane.
8, the purposes of a kind of Biodegradable polyester segmented copolymer as claimed in claim 1 is characterized in that being used for bio-medical material, drug controllable release preparation subsidiary material or environment-friendly material.
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|---|---|---|---|
| CNA2003101090990A CN1546549A (en) | 2003-12-04 | 2003-12-04 | Bio-degradability polyester block macromolecule copolymer, preparation method and uses |
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|---|---|---|---|
| CNA2003101090990A CN1546549A (en) | 2003-12-04 | 2003-12-04 | Bio-degradability polyester block macromolecule copolymer, preparation method and uses |
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Family
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|---|---|---|---|
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100523050C (en) * | 2007-08-02 | 2009-08-05 | 同济大学 | Method for preparing polylactic acid-polycarbonate copolymers |
| CN100558786C (en) * | 2007-08-02 | 2009-11-11 | 同济大学 | A kind of preparation method of polylactic acid group block copolymer |
| CN100558787C (en) * | 2007-08-02 | 2009-11-11 | 同济大学 | A kind of preparation method of full biodegradation polyester copolymer |
| CN101328259B (en) * | 2008-07-31 | 2011-07-06 | 绍兴文理学院 | Preparation of biodegradable fermentation organic acid ployester |
| CN102177192A (en) * | 2008-10-10 | 2011-09-07 | 日本电气株式会社 | Process for producing polyhydroxy polyester |
| CN103804663A (en) * | 2014-03-07 | 2014-05-21 | 中国科学院长春应用化学研究所 | Aliphatic series-polylactic acid segmented copolymer and preparation method thereof |
| CN104448259A (en) * | 2014-11-27 | 2015-03-25 | 中国科学院长春应用化学研究所 | Branching aliphatic polyester polylactic acid copolymer and preparation method thereof |
| CN105566615A (en) * | 2016-01-14 | 2016-05-11 | 常州大学 | Method for reducing yellowness index of polyglycolic acid |
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| WO2021180138A1 (en) * | 2020-03-11 | 2021-09-16 | Huang Edwin W | Self-catalyzing rapid degradable polyester polymers and preparation method and use thereof |
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2003
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100523050C (en) * | 2007-08-02 | 2009-08-05 | 同济大学 | Method for preparing polylactic acid-polycarbonate copolymers |
| CN100558786C (en) * | 2007-08-02 | 2009-11-11 | 同济大学 | A kind of preparation method of polylactic acid group block copolymer |
| CN100558787C (en) * | 2007-08-02 | 2009-11-11 | 同济大学 | A kind of preparation method of full biodegradation polyester copolymer |
| CN101328259B (en) * | 2008-07-31 | 2011-07-06 | 绍兴文理学院 | Preparation of biodegradable fermentation organic acid ployester |
| CN102177192A (en) * | 2008-10-10 | 2011-09-07 | 日本电气株式会社 | Process for producing polyhydroxy polyester |
| CN102177192B (en) * | 2008-10-10 | 2013-06-12 | 日本电气株式会社 | Process for producing polyhydroxy polyester |
| CN103804663A (en) * | 2014-03-07 | 2014-05-21 | 中国科学院长春应用化学研究所 | Aliphatic series-polylactic acid segmented copolymer and preparation method thereof |
| CN104448259A (en) * | 2014-11-27 | 2015-03-25 | 中国科学院长春应用化学研究所 | Branching aliphatic polyester polylactic acid copolymer and preparation method thereof |
| CN105566615A (en) * | 2016-01-14 | 2016-05-11 | 常州大学 | Method for reducing yellowness index of polyglycolic acid |
| WO2021180138A1 (en) * | 2020-03-11 | 2021-09-16 | Huang Edwin W | Self-catalyzing rapid degradable polyester polymers and preparation method and use thereof |
| CN112760739A (en) * | 2020-12-31 | 2021-05-07 | 扬州富威尔复合材料有限公司 | Low-melting-point polyester fiber for automotive interior and preparation method thereof |
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