CN1418901A - Carboxy polylactic acid contained composition and preparation process thereof - Google Patents
Carboxy polylactic acid contained composition and preparation process thereof Download PDFInfo
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- CN1418901A CN1418901A CN 02155474 CN02155474A CN1418901A CN 1418901 A CN1418901 A CN 1418901A CN 02155474 CN02155474 CN 02155474 CN 02155474 A CN02155474 A CN 02155474A CN 1418901 A CN1418901 A CN 1418901A
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- lactic acid
- acid
- carboxyl
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 16
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims description 20
- 239000000203 mixture Substances 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title description 16
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N Lactic Acid Natural products CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000004310 lactic acid Substances 0.000 claims abstract description 26
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 26
- 229920001577 copolymer Polymers 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 14
- 229920002472 Starch Polymers 0.000 claims abstract description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 6
- 239000008107 starch Substances 0.000 claims abstract description 6
- 235000019698 starch Nutrition 0.000 claims abstract description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 5
- 229920002678 cellulose Polymers 0.000 claims abstract description 4
- 239000001913 cellulose Substances 0.000 claims abstract description 4
- 150000001261 hydroxy acids Chemical class 0.000 claims abstract 5
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract 3
- -1 poly(hydroxybutyric acid-hydroxyvaleric acid) Polymers 0.000 claims description 31
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 235000015165 citric acid Nutrition 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims 1
- 238000005844 autocatalytic reaction Methods 0.000 claims 1
- 239000001630 malic acid Substances 0.000 claims 1
- 235000011090 malic acid Nutrition 0.000 claims 1
- 239000011975 tartaric acid Substances 0.000 claims 1
- 235000002906 tartaric acid Nutrition 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 abstract description 6
- 229960000549 4-dimethylaminophenol Drugs 0.000 abstract description 3
- 230000033228 biological regulation Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 abstract 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 abstract 2
- 239000002131 composite material Substances 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- 229920002959 polymer blend Polymers 0.000 abstract 1
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 201000007902 Primary cutaneous amyloidosis Diseases 0.000 description 8
- 229960000448 lactic acid Drugs 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229920001432 poly(L-lactide) Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 230000003292 diminished effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000012567 medical material Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 239000010839 body fluid Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- SYPAAUOZTIBVHX-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;2-hydroxypropanoic acid Chemical compound CC(O)C(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O SYPAAUOZTIBVHX-UHFFFAOYSA-N 0.000 description 1
- JRFXQKZEGILCCO-UHFFFAOYSA-N 5,5-dimethyl-1,3-dioxan-2-one Chemical compound CC1(C)COC(=O)OC1 JRFXQKZEGILCCO-UHFFFAOYSA-N 0.000 description 1
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 229920000331 Polyhydroxybutyrate Polymers 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 230000003053 immunization Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000036512 infertility Effects 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JMRZMIFDYMSZCB-UHFFFAOYSA-N morpholine-2,5-dione Chemical class O=C1COC(=O)CN1 JMRZMIFDYMSZCB-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005015 poly(hydroxybutyrate) Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- Materials For Medical Uses (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The carboxyl-contained lactic acid copolymer is one or lactic acid and natural polycarboxylic hydroxy acid. It is made up by means of direct condensation of the lactic acid and natural polycarboxyl hdyroxy acid under the action of self-catalysis of lactic acid. In the presence of DCC and DMAP the obtained copolymer can be reacted with hydrophilic macromolecular monobasis alcohol or dibasic alcohol to obtain correspondent segmented copolymer; and the composite is a polymer blend of carboxyl-contained lactic acid copolymer and one or 2-3 kinds of polylactic acid, polyethylene glycol, polyvinyl alcohol, polyhydrox butyric acid, polyhydroxy butyric acid-hydroxypentoic acid, poly epsilon-caprolactam, starch and cellulose. Said invention product possesses good biological compatibility, and has wide regulation range of hydrophilic property.
Description
Technical field
The present invention relates to biological degradation class medical material, relate to contain carboxyl poly(lactic acid) constituent and preparation method thereof in more detail.
Background technology
Poly(lactic acid) is a kind of have good biocompatibility and biodegradable polymkeric substance, can be used as the material of medical operation suture thread and preparations such as injection microcapsule, microballoon and implants through the FDA approval.In recent years, the relevant research that poly(lactic acid) is applied to aspects such as bone internal fixation material, medicament slow release preparation and tissue engineering bracket material has all obtained certain achievement.
The final product that poly(lactic acid) is degraded in human body as bio-medical material is carbonic acid gas and water, and intermediate product is a lactic acid.Lactic acid is to cause body fluid acidifying essential substance.Because the body fluid acidifying, immunizing power is suppressed and infringement and health risk.In addition, as medical material, poly(lactic acid) is a hydrophobic polymer, and its degradation rate is difficult to regulation and control, studies focus greatly so relevant study on the modification to poly(lactic acid) becomes one of this field.Studying more method of modifying is activation and the modification that copolymerization, blend reach the surface of being undertaken by physical adsorption.And this wherein to study relatively what concentrate mainly be copolymerization, by reactive mode and introduce the second monomeric position and can be divided into random, grafting and block copolymerization.Graft copolymerization polymkeric substance commonly used mostly is some natural polymers greatly, as starch, Mierocrystalline cellulose etc. [1. by an outstanding person, Zhu Changying, Jiao Jingliang, Shen Xin, the synthetic and biodegradability research of starch/DL-rac-Lactide graft copolymer, the polymer journal, 2000,6:746-750.2.Ohya?Y，Maruhashi?S，Ouchi?T.Graft?Polymerization?of?L-Lactide?on?pullulan?through?the?TrimethylsiylProtection?method?and?Degradation?of?the?Graft?Copolymers，Macromolecules?1998，31(14)：4662-4665。3.Ohya?Y，Mamhashi?S，Ouchi?T.Preparation?of?Poly(lacticacid)-grafted?Amylose?through?the?Trimethylsilyl?Protection?Method?and?itsBiodegradation，Macromol.Chem.Phys.，1998，199(9)：2017-2022]。And the commonplace monomer that block copolymerization is used comprises oxyacetic acid, the alcohol acid of amino acid and other type [1.Jorres V, Keul H, Hocker H.Aminolysis of α-Amino Acid Salts:First Step in the Synthesis ofOptically Active 2,5-Morpholinediones, Macromol.Chem.Phys., 1998,199:825-8332.Schmidt P, Keul H, Hocker H.Copolymerization of 2,2-DimethyltrimethyleneCarbonate and L-lactide, Macromolecules, 1996,29:3674-3680.3.Vert?M，lenz?R?W.Preparation?and?Properties?of?Poly-β-malic?Acid：A?Functional?Polyester?of?PotentialBiomedical?Importance，Polymer?Preprints，1979，20：608-611]。And copolymerization process commonly used mainly concentrates on the method for ring-opening polymerization.This method is long because of synthetic route, synthesis yield is low, molecular weight of product is low and chain structure is wayward etc., and shortcoming causes its modification narrow range.
Summary of the invention
The object of the present invention is to provide a series of carboxyl lactide acid polymer and constituents thereof of containing.
The present invention also aims to provide a kind of preparation method who contains the polylactic acid-based constituent of carboxyl.Poly(lactic acid) is carried out modification, and the preparation hydrophilic/hydrophobic is adjustable, does not cause inflammatory reaction, and the degradation rate of material can be regulated and with the biological degradation medical material that is complementary of growth velocity of tissue.
Contain following listed two or more following structural unit on the molecular chain that contains the carboxyl lactic acid copolymer among the present invention:
Wherein Z is-OH ,-COOH ,-NH
2, m, n=0～8,
Its composition is the blend that contains a kind of in carboxyl lactic acid copolymer and poly(lactic acid), polyoxyethylene glycol, polyvinyl alcohol, polyhydroxybutyrate, polyhydroxybutyrate-hydroxypentanoic acid, poly-epsilon-caprolactone, starch and the Mierocrystalline cellulose or 2～3 kinds.The mass ratio that wherein contains the carboxyl lactic acid copolymer is 0.5～99.9%, is preferably 10～50%.
The preparation that contains the carboxyl lactic acid copolymer among the present invention is with lactic acid and natural many carboxyls alcohol acid, under the self-catalysis of lactic acid, in 120～180 ℃ of temperature, under pressure 20～760mmHg condition, and carry out polyreaction preparation with feeding intake of lactic acid and many carboxyls alcohol acid mol ratio 800～5: 1, the multipolymer that gained contains carboxyl lactic acid copolymer and wetting ability macromolecule dihydric alcohol then is in the presence of DCC and DMAP, and with mol ratio 10～0.1: 1 feeds intake carries out condensation reaction and prepare.
Used natural many carboxyls alcohol acid is selected from citric acid, oxysuccinic acid, tartrate among the present invention; Wetting ability macromolecule dihydric alcohol or monohydroxy-alcohol are selected from polyoxyethylene glycol, PEP-101, four Hydrogen furans polyether Glycols.
The mol ratio of lactic acid and natural many carboxyls alcohol acid is 100～10: 1 among the present invention; The mol ratio of lactic acid and wetting ability macromolecular alcohol is 2～0.5: 1.
Among the present invention, the preparation method who contains carboxyl lactic acid analog copolymer is:
Lactic acid, many carboxyls alcohol acid are added in the reactor, under the nitrogen protection, be heated to 120 ℃; normal pressure reacted 1～4 hour down, slowly was decompressed to 20mmHg, continued reaction 3～5 hours; system is continued to be decompressed to 1～2mmHg, and temperature rises to 150～180 ℃, continues reaction 3～5 hours.Polymkeric substance is dissolved with chloroform, ether sedimentation, vacuum-drying, product is a white fiber shape solid.
The present invention compared with prior art has following advantage:
1, by melt-polycondensation, make and contain carboxyl lactic acid analog copolymer, preparation section is simple, and condition is easy to control, by the adjusting of several comonomer consumptions, the degradation rate of gained multipolymer, hydrophilic/hydrophobic is regulated in a big way.
2, have better biocompatibility, wetting ability is strong, helps adhesion, growth and the breeding of cell.
3, by containing blend such as carboxyl lactic acid analog copolymer and other polymkeric substance such as poly(lactic acid), polyoxyethylene glycol, starch, can make the degradable biological medical material of high comprehensive performance.
4, eliminated the bacillary and sterility reaction that traditional material exists.
Below by embodiment the present invention is further described below.
Embodiment one
PLCA's is synthetic: a certain amount of 88%L-lactic acid (LA) was mixed with citric acid (CA) in 24: 1 in molar ratio, in 150 ℃ of following synthesis under normal pressure 2h, 1.3 * 10
4Pa is reaction 2h down, and 4.0 * 10
3Pa is reaction 4h down, obtains yellow thick L-lactic acid and citric acid oligopolymer.Then add the SnCl of quality for this oligopolymer 0.4%
22H
2O is heated to 150 ℃, progressively is decompressed to 1.06 * 10
3Pa, reaction 8h.After above-mentioned product is cooled to room temperature, with acetone solution, water precipitation, and with behind a large amount of deionized water repetitive scrubbings, filtration under diminished pressure, under 40 ℃ in vacuum drying oven dry 48h, obtain yellow powder shape product P LCA at last.Its
[COOH]=1.52 * 10
-3Mol/g, Tg=47.4 ℃, Tm=130.16 ℃, its degradation rate is obviously faster than PLLA.
Embodiment two
The preparation of hydroxyl-terminated polylactic acid: with 100g L-lactic acid (88% aqueous solution) and a certain amount of 1, the 6-hexylene glycol mixes, 150 ℃ of following synthesis under normal pressure 2h, 1.3 * 10
4Pa is reaction 2h down, and 4.0 * 10
3Pa is reaction 4h down, gets light yellow thick oligopolymer.Adding quality is the SnCl of this oligopolymer 0.4%
22H
2O is at 160 ℃, 1.06 * 10
3React 8h under the condition of Pa.
In acetone, with a large amount of distilled water product that settles out, behind the filtration under diminished pressure, dry 48h gets the white powder solid in 40 ℃ of following vacuum drying ovens then with cooled above-mentioned reactants dissolved.
Embodiment three
The preparation of PLCA-PEG segmented copolymer: PLCA and the equimolar PEG of 1mmol are dissolved in the 70ml methylene dichloride, add the catalyzer DMAP of 0.25mmol and the coupling agent DCC of 5mmol, induction stirring 24h under the normal temperature.Elimination byproduct of reaction DCU, filtrate is poured in the excessive ether after concentrating.Behind the filtration under diminished pressure, products therefrom is placed vacuum drying oven, Air drying 48h gets light brown pulverulent solids.Mw=7600, Tg=20.6 ℃, with the contact angle of water be 45 °, water-intake rate is 151%, tensile strength is 8.33MPa, elongation at break is 7.6%.
Embodiment four
The preparation of PLLA/PLCA co-mixing system:
PLLA and PLCA are dissolved in the chloroform in 1: 1 ratio and make film forming liquid, its concentration is controlled at 10g polymkeric substance/100 solvents.Film forming liquid is cast in the tetrafluoroethylene mould of 12cm * 12cm, behind the dry 24h of normal temperature and pressure, 5 * 10
4Dry 12h under the Pa, 1 * 10
4Pa continues down to take out after the dry 12h constant weight, and the mean thickness of measuring film is about 0.14mm, is cut into to put into moisture eliminator behind the small pieces of 10mm * 20mm and preserve.Tg=52.7 ℃, Tm=145.2 ℃, with the contact angle of water be 52 °, water-intake rate is 130%, the purer poly(lactic acid) of degradation rate is fast, and is slow than lactic acid-citric acid multipolymer.
Embodiment five
PLLA, PEG and different PLCA are dissolved in the chloroform in 59.5: 25.5: 15 ratio and make film forming liquid, its concentration is controlled at 10g polymkeric substance/100ml solvent.Film forming liquid is cast in the tetrafluoroethylene mould of 12cm * 12cm, behind the dry 24h of normal temperature and pressure, 5 * 10
4Dry 12h under the Pa, 27Pa continue down to take out after the dry 12h constant weight, and the mean thickness of measuring film is about 0.14mm, are cut into to put into moisture eliminator behind the small pieces of 10mm * 20mm and preserve.Tg=15.8 ℃, Tm
1=61.54 ℃, Tm
2=149.47 ℃, with the contact angle of water be 63 °, tensile strength is 11.6MPa.
Embodiment six
Adding PVA and solvent in the there-necked flask of 250ml are heated with stirring to 100 ~ 140 ℃ and make the PVA dissolving, are cooled to then about 120 ℃ to add PLLA, controlled temperature is no more than 120 ℃ and makes the PLLA dissolving, be cooled to 40 ℃, add PLCA, treat that it all dissolves the back filtration under diminished pressure and promptly makes film forming liquid.Film forming liquid is poured in the tetrafluoroethylene mould, under 45 ℃, allowed its solvent evaporates 7 days, 45 ℃ of following 2 weeks of vacuum-drying.The thickness of film is about 0.07mm.PLLA/PVA/PLCA=18/72/10, tensile strength is 25MPa (doing), 18.5MPa (wetting), elongation at break are 150%, water-intake rate is 520%, with the contact angle of water be 85 °, degradation rate is formed different because of system.
Claims (5)
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| CN 02155474 CN1418901A (en) | 2002-12-16 | 2002-12-16 | Carboxy polylactic acid contained composition and preparation process thereof |
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100372881C (en) * | 2006-08-10 | 2008-03-05 | 同济大学 | A kind of preparation method of biodegradable polyester copolymer |
| CN100384936C (en) * | 2005-12-08 | 2008-04-30 | 上海林达塑胶化工有限公司 | Preparation method of composite biodegradable masterbatch |
| CN100406498C (en) * | 2006-03-09 | 2008-07-30 | 四川大学 | Polyvinyl alcohol/polylactic acid graft copolymer and its blended material with starch, its preparation method and use |
| CN100558795C (en) * | 2006-09-07 | 2009-11-11 | 同济大学 | Preparation method of fully biodegradable polylactic acid-based multi-block polymer |
| CN104098774A (en) * | 2013-04-15 | 2014-10-15 | 江南大学 | Preparation method of magnetic-response star-type segmented copolymer nano-micelle as drug carrier |
| CN111905147A (en) * | 2020-08-17 | 2020-11-10 | 刘小雄 | Injection material for beauty and plastic and injection method thereof |
| CN115926122A (en) * | 2022-12-23 | 2023-04-07 | 浙江海正生物材料股份有限公司 | Method for preparing polylactic acid-polyvinyl alcohol graft copolymer |
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2002
- 2002-12-16 CN CN 02155474 patent/CN1418901A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100384936C (en) * | 2005-12-08 | 2008-04-30 | 上海林达塑胶化工有限公司 | Preparation method of composite biodegradable masterbatch |
| CN100406498C (en) * | 2006-03-09 | 2008-07-30 | 四川大学 | Polyvinyl alcohol/polylactic acid graft copolymer and its blended material with starch, its preparation method and use |
| CN100372881C (en) * | 2006-08-10 | 2008-03-05 | 同济大学 | A kind of preparation method of biodegradable polyester copolymer |
| CN100558795C (en) * | 2006-09-07 | 2009-11-11 | 同济大学 | Preparation method of fully biodegradable polylactic acid-based multi-block polymer |
| CN104098774A (en) * | 2013-04-15 | 2014-10-15 | 江南大学 | Preparation method of magnetic-response star-type segmented copolymer nano-micelle as drug carrier |
| CN111905147A (en) * | 2020-08-17 | 2020-11-10 | 刘小雄 | Injection material for beauty and plastic and injection method thereof |
| CN115926122A (en) * | 2022-12-23 | 2023-04-07 | 浙江海正生物材料股份有限公司 | Method for preparing polylactic acid-polyvinyl alcohol graft copolymer |
| CN115926122B (en) * | 2022-12-23 | 2024-05-14 | 浙江海正生物材料股份有限公司 | Method for preparing polylactic acid-polyvinyl alcohol graft copolymer |
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