CN101134807A - Polylactic acid radical biological degradable material and method for preparing same - Google Patents
Polylactic acid radical biological degradable material and method for preparing same Download PDFInfo
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Abstract
The present invention belongs to the field of biodegradable material preparing and modifying technology, and is especially one kind of polylactic acid-based biodegradable material and its preparation process. The polylactic acid-based biodegradable material is prepared with lactide, tin catalyst/initiator and end hydroxyl group co-initiator in certain molar ratio and through polymerization in a reaction kettle inside nitrogen atmosphere at 110-180 deg.c for 8-20 hr. The polymer has rigid segment or flexible segment accounting for 0.1-30 mol% weight average molecular weight greater than 150,000, and possesses biodegradability, improved flexibility, raised shock resistance, etc. The present invention provides one new way for the copolymerizing modification of polylactic acid.
Description
Invention field
The invention belongs to the preparation and the modification technology field of Biodegradable material, be specifically related to a kind of polylactic acid radical biological degradable material and preparation method thereof.
Background technology
Along with the exhaustion day by day of petroleum resources and the continuous rising of oil price, the plastics industry that with the oil is raw material is faced with the immense pressure that raw material exhausts to be increased with cost, add that white pollution is remarkable day by day to the harm of environment, become the focus of people's research so that biomass are the degradation material of raw material.
Poly(lactic acid) (Poly lactic acid, PLA) be to be monomer and a base polymer of chemosynthesis with microbial fermentation product lactic acid, be a kind of nontoxic, nonirritant, have the linear biodegradated polymer materal of polyester of good biocompatibility, biodegradable absorption.Lactic acid can be obtained by amylofermentation, and starch source is extensive, and reproducible natural phant all can be used as its raw material as Ipomoea batatas, corn and other cereal.Polylactic resin can be by monomer lactic acid cyclisation synthesis of lactide from, and rac-Lactide ring-opening polymerization again is synthetic, or can be obtained by the lactic acid direct polymerization.But its property is crisp, impact-resistance is poor, reaches shortcomings such as thermolability, makes its application be subjected to certain limitation.So the study on the modification of poly(lactic acid) is subject to people's attention gradually.
Aspect the modification of poly(lactic acid) copolymerizing and blending, some researchs have also been done both at home and abroad.
The disclosed poly(lactic acid) of the patent documentation high-molecular weight polymer that can't obtain having the good physical mechanical property in early days.Patent US1995970, US2362511 and US2668162 disclose the multipolymer of a kind of rac-Lactide and glycollide, and this multipolymer toughness is good, can be cold drawn, but drawing-off.US4661530 discloses the mixture of a kind of poly(lactic acid) and block polyester carbamate or polyethers carbamate, and this kind biodegradable material can be used as the alternative synthetics of biological tissue and organ in the plastic surgery.
CN1922270 discloses a kind of biodegradable polymer composition, its comprise the poly(lactic acid) of mixing organo-peroxide and particles of inorganic material and with the copolyester polymer of hexanodioic acid copolymerization.CN1827665 discloses a kind of lactide open-ring polymerization catalyst, comprise Schiff's base aluminum alkyls and aluminum alkoxide catalyzer and method for making thereof, provide a kind of by 3,5-dichloro-salicylaldehyde and diamines set out, synthetic schiff base ligand, and then the method for synthetic Schiff's base aluminum alkyl catalyst.CN1418901 discloses and has contained carboxyl poly(lactic acid) constituent and manufacture method thereof.CN1491988 discloses a kind of poly(lactic acid)/amino acid ester blend and preparation method thereof, and blend is to adopt the solution blended process polydactyl acid.CN1108669 discloses the method for preparing poly(lactic acid), comprising: step (a): use the rac-Lactide of doing main raw material in the molten state polymerization, obtain poly(lactic acid); (b), make the poly(lactic acid) that obtains in the step (a) in the further polymerization of solid phase by temperature heating at the fusing point that is lower than final polymer product.CN1159462 discloses the plasticized polymer of polylactide and blend thereof, also relates to a kind of material that can be used as the crystal polystyrene surrogate and preparation method thereof in addition.The third aspect relates to conventional thermoplastics and polylactic acid blend, prepares new packaging material.Fourth aspect is about with compatible elastomerics and polylactide blend, obtains impact-resistant modified polylactide.CN1476459 discloses high-molecular aliphatic polyester multipolymer, poly lactic acid series high-molecular aliphatic polyester multipolymer, its manufacture method, their composition and various uses.
More than various method of modifying focus mostly on aspect blending and modifying, about modification by copolymerization mostly by rac-Lactide and other annular unit ring opening copolymers.And the present invention has synthesized the segmented copolymer of polylactic acid chain segment and other polymer segments by the control to initiator.
Summary of the invention
The object of the present invention is to provide a kind of polylactic acid radical biological degradable material and preparation method thereof.
The polylactic acid radical biological degradable material that the present invention proposes, with the pink salt class is initiator/catalyst, hydroxy-terminated polymer is a coinitiator, form by the rac-Lactide ring-opening polymerization, the molar ratio that rigid chain segment in this polymkeric substance (as phenyl ring) or soft segment (as PEG, PCL) account for polymkeric substance is 0.1%-30%, the polymkeric substance weight-average molecular weight is greater than 150000, and its configuration is as follows:
Wherein, R is arbitrary to several in aliphatic polyester, aromatic polyester, macrogol ester (PEG), polycarbonate, polycaprolactone (PCL) or the starch etc.
Among the present invention, described aliphatic polyester be in poly butylene succinate (PBS), poly adipate succinic acid ester (PBA), polyethylene glycol succinate, polyethylene glycol adipate or the poly-isoamyl diacid butanediol ester etc. any; Described aromatic polyester be in poly terephthalic acid-Succinic Acid-butanediol ester, adipic acid, butanediol ester, poly-phthalic acid butanediol ester or the poly-m-phthalic acid butanediol ester etc. any.
The present invention is with Sn (Oct)
2/ ROH is that catalyst causes the rac-Lactide ring-opening polymerization.Reaction beginning generates the RO-Sn-Oct structure earlier, is initiator with RO-Sn-Oct then, produces fast initiation reaction, and knows from reaction kinetics, and the polymerization degree is living polymerization 80% when following, can effectively introduce cosegment.This triggering mechanism altogether provides theoretical foundation for the present invention utilizes hydroxy-terminated polymer for the polylactic acid based block copolymerization material of coinitiator synthesized degradable.
The invention discloses a kind of method of polylactic acid group block copolymer of synthetic macromolecule amount.Require this polymericular weight more than 100,000, can satisfy fiber, blown film, the needs of processing such as injection moulding.In addition,, require tensile property because different segmental is introduced, Young's modulus, erosion-resisting characteristics and resistance toheat etc. increases.
The preparation method of the polylactic acid radical biological degradable material that the present invention proposes, its concrete steps are as follows:
To place reactor through the purified rac-Lactide, under pink salt class catalyst and the effect of terminal hydroxy group coinitiator, polymerization reaction take place, vacuumize, under nitrogen atmosphere, by 8 ℃ of-12 ℃/30min heat-up rates, be heated to 110-180 ℃, and under this temperature, reacted 8～20 hours, promptly get required product; Wherein, the mol ratio of rac-Lactide and pink salt class catalyst is 100: 1-1000: 1, and the mol ratio of rac-Lactide and terminal hydroxy group coinitiator is 10: 1-100: 1.
Among the present invention, the refining of described rac-Lactide comprehensively uses for any or several method in WATER-WASHING METHOD, recrystallization method or the boiling point partition method.
Among the present invention, described rac-Lactide is L-rac-Lactide, D-rac-Lactide or D, in the L-rac-Lactide any, preferred D, L-rac-Lactide.
Among the present invention, described pink salt class catalyst is Sn (Oct)
2, SnCl
2, SnCl
4Or SnBr
2Deng in any, preferred Sn (Oct)
2
Among the present invention, described terminal hydroxy group coinitiator for be the aliphatic polyester that generates of monomer reaction with diprotic acid and dibasic alcohol, with the alcohol acid be aliphatic polyester, terminal hydroxy group aliphatics degradable poly acid amides, the diprotic acid that contains phenyl ring and dibasic alcohol that monomer reaction generates be in aromatic polyester, polyoxyethylene glycol (PEG), polycaprolactone (PCL) or the starch etc. of monomer reaction generation any.
Among the present invention, described is that the aliphatic polyester that monomer reaction generates is poly butylene succinate (PBS), poly adipate succinic acid ester (PBA), polyethylene glycol succinate with diprotic acid and dibasic alcohol, in polyethylene glycol adipate or the poly-isoamyl diacid butanediol ester etc. any, preferred poly butylene succinate.
Among the present invention, described is the aliphatic polyester that monomer reaction generates with the alcohol acid, monomer be in oxyacetic acid, lactic acid, 3-hydroxybutyric acid, 4 hydroxybutyric acid, 3-hydroxypentanoic acid, 4-hydroxypentanoic acid or the 6 hydroxycaproic acid etc. any, preferred polyglycolic acid.
Among the present invention, described terminal hydroxy group aliphatics degradable poly acid amides is bisamide-glycol that the reaction of bisamide and lactone (alcohol acid) obtains, in terminal hydroxy group polyimide or the terminal hydroxy group polycaprolactam etc. any, preferred terminal hydroxy group hexanolactam.
Among the present invention, terminal hydroxy group aromatic series degradable polyester comprises:
With the diprotic acid that contains phenyl ring and dibasic alcohol be aromatic polyester that monomer reaction generates be in poly terephthalic acid-Succinic Acid-butanediol ester, poly terephthalic acid-hexanodioic acid-butanediol ester, poly-phthalic acid butanediol ester or the poly-m-phthalic acid butanediol ester etc. any to three kinds.Preferred poly terephthalic acid-hexanodioic acid-butanediol ester.
The present invention is the reaction product toughness increase of coinitiator with the terminal hydroxy group aliphatic polyester, and it is big that elongation at break becomes, and this is because poly(lactic acid) homopolymer molecular chain is rigidity, so the insufficient weakness of poly(lactic acid) flexible.But coinitiator has been introduced soft segment when the polylactic acid molecule amount is improved, played toughening effect.So multipolymer toughness increases, it is big that elongation at break becomes.
The present invention is the reaction product thermotolerance increase of coinitiator with the terminal hydroxy group aromatic polyester, and melt temperature and heat decomposition temperature increase.Degree of crystallinity reduces along with the increase of phenyl ring introducing amount, makes degradation property rise.Yet when phenyl ring content was excessive, benzene ring structure accounted for essential factor, and degradation property is descended.So the present invention requires multipolymer phenyl ring molar content to be lower than 30%.
The result shows that the present invention is obtaining on the basis of poly-lactic acid in high molecular weight, by introducing the variation of segment kind and content, has accomplished polylactic acid modified control.On this basis, can adopt spinning to the polymkeric substance that makes, complete processings such as blowing mould obtain well behaved Biodegradable material.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1
Sn (Oct) with the refined L-rac-Lactide of 30mol, 0.3mol
2, 0.3mol poly butylene succinate join in the reactor, vacuumize, logical nitrogen gets rid of the air in the reactor three times repeatedly, under the environment of logical nitrogen (3L/min), heat up gradually (8 ℃/30min) to 160 ℃ of reactions 20 hours.Obtain weight-average molecular weight and be 198,000 polymkeric substance.
Embodiment 2
With the refined D of 30mol, the SnCl of L-rac-Lactide, 0.03mol
2, 0.3mol poly butylene succinate join in the reactor, vacuumize, logical nitrogen gets rid of the air in the reactor three times repeatedly, under the environment of logical nitrogen (3L/min), heat up gradually (10 ℃/30min) to 140 ℃ of reactions 20 hours.Obtain weight-average molecular weight and be 215,000 polymkeric substance.
Embodiment 3-7
With the refined D of 30mol, the Sn of L-rac-Lactide, 0.03mol (Oct)
2, a certain amount of poly butylene succinate joins in the reactor, vacuumizes, logical nitrogen gets rid of the air in the reactor three times repeatedly, under the environment of logical nitrogen (3L/min), heat up gradually (12 ℃/30min) to 160 ℃ of reactions 20 hours.
| Poly butylene succinate | The products therefrom polymericular weight | |
| Embodiment 3 | 0.3mol | 215,000 |
| Embodiment 4 | 1mol | 197,000 |
| Embodiment 5 | 2mol | 183,000 |
| Embodiment 6 | 5mol | 164,000 |
| Embodiment 7 | 9mol | 150,600 |
Embodiment 8-12
With the refined D of 30mol, the Sn of L-rac-Lactide, 0.03mol (Oct)
2, 0.3mol poly butylene succinate join in the reactor, vacuumize, logical nitrogen gets rid of the air in the reactor three times repeatedly, under the environment of logical nitrogen (3L/min), heat up (10 ℃/30min) reaction 20 hours under the certain temperature gradually.
| Temperature of reaction ℃ | Polymericular weight | |
| Embodiment 8 | 110 | 136,000 |
| Embodiment 9 | 120 | 152,000 |
| Embodiment 10 | 140 | 173,800 |
| Embodiment 11 | 160 | 215,000 |
| Embodiment 12 | 180 | 198,200 |
Embodiment 13
SnCl with the refined L-rac-Lactide of 30mol, 0.03mol
4, 0.3mol poly terephthalic acid-hexanodioic acid-butanediol ester join in the reactor, vacuumize, logical nitrogen gets rid of the air in the reactor three times repeatedly, under the environment of logical nitrogen (3L/min), heat up gradually (10 ℃/30min) to 160 ℃ of reactions 20 hours.Obtain weight-average molecular weight and be 201,000 polymkeric substance.
Embodiment 14-18
Sn (Oct) with the refined L-rac-Lactide of 30mol, 0.03mol
2, 0.3mol coinitiator join in the reactor, vacuumize, logical nitrogen gets rid of the air in the reactor three times repeatedly, under the environment of logical nitrogen (3L/min), heat up gradually (10 ℃/30min) to 160 ℃ of reactions 10 hours.Obtain weight-average molecular weight and be 169,000 polymkeric substance.
| Coinitiator | Polymericular weight | |
| Embodiment 14 | Polyoxyethylene glycol | 176,000 |
| Embodiment 15 | Polycaprolactone | 152,800 |
| Embodiment 16 | Poly adipate succinic acid ester | 163,200 |
| Embodiment 17 | Poly terephthalic acid-Succinic Acid-butanediol ester | 174,600 |
| Embodiment 18 | Poly-phthalic acid butanediol ester | 225,000 |
Claims (8)
1. polylactic acid radical biological degradable material, it is characterized in that with the pink salt class be initiator/catalyst, hydroxy-terminated polymer is a coinitiator, form by the rac-Lactide ring-opening polymerization, to account for the molar ratio of polymkeric substance be 0.1%-30% for rigid chain segment or soft segment in this polymkeric substance, the polymkeric substance weight-average molecular weight is greater than 150000, and its configuration is as follows:
Wherein, R is with arbitrary to several in aliphatic polyester, aromatic polyester, macrogol ester, polycarbonate, polycaprolactone or the starch.
2. polylactic acid radical biological degradable material according to claim 1, it is characterized in that aliphatic polyester be in poly butylene succinate, poly adipate succinic acid ester, polyethylene glycol succinate, polyethylene glycol adipate or the poly-isoamyl diacid butanediol ester any; Described aromatic polyester be in poly terephthalic acid-Succinic Acid-butanediol ester, hexanodioic acid, butanediol ester, poly-phthalic acid butanediol ester or the poly-m-phthalic acid butanediol ester any.
3. the preparation method of a polylactic acid radical biological degradable material as claimed in claim 1 is characterized in that concrete steps are as follows:
To place reactor through the purified rac-Lactide, under pink salt class catalyst and the effect of terminal hydroxy group coinitiator, polymerization reaction take place, vacuumize, under nitrogen atmosphere, by 8 ℃ of-12 ℃/30min heat-up rates, be heated to 110～180 ℃, and under this temperature, reacted 8～20 hours, promptly get required product; Wherein, the mol ratio of rac-Lactide and pink salt class catalyst is 100: 1-1000: 1, and the mol ratio of rac-Lactide and terminal hydroxy group coinitiator is 10: 1-100: 1.
4. the preparation method of polylactic acid radical biological degradable material according to claim 3 is characterized in that the refining of described rac-Lactide is that one or more method synthesis use in WATER-WASHING METHOD, recrystallization method or the boiling point partition method.
5. the preparation method of polylactic acid radical biological degradable material according to claim 3 is characterized in that described rac-Lactide is L-rac-Lactide, D-rac-Lactide or D, in the L-rac-Lactide any.
6. the preparation method of polylactic acid radical biological degradable material according to claim 3 is characterized in that described pink salt class catalyst is Sn (Oct)
2, SnCl
2, SnCl
4Or SnBr
2In any.
7. the preparation method of polylactic acid radical biological degradable material according to claim 3, it is characterized in that described terminal hydroxy group coinitiator for be the aliphatic polyester that generates of monomer reaction with diprotic acid and dibasic alcohol, with the alcohol acid be aliphatic polyester, terminal hydroxy group aliphatics degradable poly acid amides, the diprotic acid that contains phenyl ring and dibasic alcohol that monomer reaction generates be in aromatic polyester, polyoxyethylene glycol, polycaprolactone or the starch of monomer reaction generation any.
8. the preparation method of polylactic acid radical biological degradable material according to claim 7, it is characterized in that described with diprotic acid and dibasic alcohol be aliphatic polyester that monomer reaction generates be in poly butylene succinate, poly adipate succinic acid ester, polyethylene glycol succinate, polyethylene glycol adipate or the poly-isoamyl diacid butanediol ester any; Described is the aliphatic polyester that monomer reaction generates with the alcohol acid, monomer be in oxyacetic acid, lactic acid, 3-hydroxybutyric acid, 4 hydroxybutyric acid, 3-hydroxypentanoic acid, 4-hydroxypentanoic acid or the 6 hydroxycaproic acid any; Described terminal hydroxy group aliphatics degradable poly acid amides is bisamide-glycol that the reaction of bisamide and lactone (alcohol acid) obtains: in terminal hydroxy group polyimide or the terminal hydroxy group polycaprolactam any; With the diprotic acid that contains phenyl ring and dibasic alcohol be aromatic polyester that monomer reaction generates be in poly terephthalic acid-Succinic Acid-butanediol ester, poly terephthalic acid-hexanodioic acid-butanediol ester, poly-phthalic acid butanediol ester or the poly-m-phthalic acid butanediol ester any to three kinds.
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