CN100535033C - Polylactic-acid block copolymer and preparation method thereof - Google Patents
Polylactic-acid block copolymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a poly-lactic acid block copolymer. The feature is that it is made from the end hydroxyl poly-lactic acid with intrinsic viscosity of 0.05-0.5dL/g and aliphatic polyester glycol with intrinsic viscosity of 0.1-1.0dL/g taking fusion reaction under existing of diisocyanate. The intrinsic viscosity of the copolymer is 0.7-2.5dL/g, and tensile strength is 10-40MPa, elongation at break is 100-800%. The invention also discloses the manufacturing method for the copolymer. It has the advantages of good toughness, strong tensile strength, high tensile fracture elongation, etc.
Description
Technical field
The invention belongs to poly(lactic acid) modification by copolymerization technical field, be specifically related to a kind of polylactic-acid block copolymer and preparation method thereof.
Background technology
At present, the commodity polymer Development of Materials is being faced with two challenges greatly: the one, and the price increase that causes owing to the shortage of petroleum resources; The 2nd, the environmental pollution that causes owing to difficult degradation.In order to solve this two large problems, in recent years, become the hot subject of Chinese scholars research from the degradable macromolecular material of renewable resources preparation.
Poly(lactic acid) is a kind of reproducible biodegradable material, the lactic acid that it normally obtains with amylofermentation is that the basic raw material preparation gets, have excellent biocompatibility, biological degradability and Bioabsorbable, and all nontoxic to human body and environment, be described as the bio-medical material that has future.But the poly-lactic acid in high molecular weight that can use as material is to get by the rac-Lactide ring-opening polymerization mostly the earliest, as U.S.2,758,987 disclosed indirect methods prepare the synthesis technique of poly-lactic acid in high molecular weight, earlier make the cyclic monomer rac-Lactide, make poly-lactic acid in high molecular weight by the refined lactide ring-opening polymerization then by the acid by dehydrating lactic cyclisation.The poly(lactic acid) that this method makes is because complicated process of preparation, cost height, range of application are confined to special dimensions such as medical material substantially, and poly(lactic acid) is because the self structure lacking toughness in addition, tension fracture elongation rate low (less than 10%) has limited its use as general purpose material.Therefore improve toughness and reduce cost and become the striving direction of poly(lactic acid) research work.
In addition, poly(lactic acid) can prepare (Yaoming Zhao by melt-polycondensation, Zhaoyang Wang, JunWang.J Appl Polym Sci 2004 (91): 2143～2150), though this method can reduce cost greatly, but the polylactic acid molecule amount that makes is generally lower, and over-all properties is poor, and purposes is narrow.(KARIHILTUNEN, JUKKA V. such as KARI HILTUNEN
MIKA
J Appl Polym Sci 1997 (63): 1091～1100) though adopt first polycondensation again the method preparation of chain extension obtained the poly(lactic acid) of lower cost, higher molecular weight, its mechanical property is not ideal enough, tension fracture elongation rate only is 3.2%.
For toughness and the tension fracture elongation rate that improves poly-lactic acid material, expand the range of application of poly(lactic acid) in the general-purpose plastics field, numerous Chinese scholars have been carried out the research work of copolymerization method polydactyl acid.U.S.5,342,395, U.S.5,631,344, U.S.5,633,342, U.S.4,243,775 grades have described rac-Lactide and other monomer copolymerization prepares the high-molecular weight multipolymer, though these multipolymers have good performance, but because complex process, production cycle is long, the cost height, and range of application has been subjected to greatly restriction.(Yuqing Wan such as Yuqing Wan, Wenna Chen, Jian Yang.Biomaterials 24 (2003): 2195～2203) adopting polyoxyethylene glycol is that the ring-opening polymerization of macromonomer initiation rac-Lactide prepares the PLA-PEG-PLA triblock copolymer, make solvent with methylene dichloride then, Succinic anhydried and dicyclohexyl carbodiimide are coupling agent, Dimethylamino pyridine is that catalyzer at room temperature reacts and prepared the maximum tension elongation at break in 48 hours and can reach 734% PLA-PEG segmented copolymer, yet this complex synthetic route, and also introduced solvent in the reaction system, inevitably increased the cost of product, its range of application also only is confined to special dimensions such as medical material.(Chaoyi Ba such as Chaoyi Ba, Jing Yang, Qinghui Hao.Biomacromolecules 2003 (4): 1827～1834) adopting the poly butylene succinate glycol is that macromonomer causes the rac-Lactide ring-opening polymerization, prepared the PLA-PBS-PLA triblock copolymer, but article is not described to the mechanical property of multipolymer.D.Cohn etc. (D.Cohn, A.Hotovely Salomon.Polymer 2005 (46): 2068～2075; D.Cohn, A.HotovelySalomon.Biomaterials 2005 (26): 2297～2305) adopt polyoxyethylene and polycaprolactone to cause the rac-Lactide ring-opening polymerization as macromonomer respectively and prepared PLA-PEO-PLA and PLA-PCL-PLA triblock copolymer, and then prepared PLA-PEO and PLA-PCL segmented copolymer with these two kinds of multipolymers and di-isocyanate reaction respectively.Because this synthetic route also fails to avoid the ring-opening polymerization of rac-Lactide, causes the cost of product also higher.Janne
Deng (Janne
Jukka V.
Macromolecules 1997 (30): what 2876～2882) then adopt is the random copolymers that generates terminal hydroxy group earlier with butyleneglycol, lactic acid monomer and caprolactone monomer reaction, and then with this multipolymer and di-isocyanate reaction.Though this method has obtained the quite high thermoplastic elastomer of elongation at break, the randomness of its structure causes its tensile strength usually less than 2.0MPa.
Summary of the invention
At the deficiencies in the prior art, it is low to the purpose of this invention is to provide a kind of cost, has simultaneously that tensile strength is big, tension fracture elongation rate is high and the polylactic-acid block copolymer of advantage such as degradable.
Another object of the present invention is the method that the above-mentioned polylactic-acid block copolymer of preparation is provided simultaneously.
Polylactic-acid block copolymer provided by the invention, it is characterized in that this multipolymer is that the hydroxyl-terminated polylactic acid of 0.05～0.5dL/g and aliphatic poly esterdiol that intrinsic viscosity is 0.1～1.0dL/g get through the frit reaction preparation in the presence of the chainextender vulcabond by intrinsic viscosity, its repeating structure is as follows:
Wherein PLA represents polylactic acid chain segment, APE
1, APE
2Represent two kinds of different aliphatic polyester segments, R represents the structure of hydrocarbyl portion in the chainextender vulcabond, and the intrinsic viscosity of this multipolymer is 0.7～2.5dL/g, and tensile strength is 10～40MPa, and elongation at break is 100～800%.
The method of the above-mentioned polylactic-acid block copolymer of preparation provided by the invention is as prepolymer with hydroxyl-terminated polylactic acid and aliphatic poly esterdiol; it is even to be warmed up to 130～200 ℃ of stirring melting mixing under protection of inert gas; add the chainextender vulcabond then 130～200 ℃ of reactions 3～120 minutes; or with hydroxyl-terminated polylactic acid; aliphatic poly esterdiol and chainextender are together after the pre-mixing; under nitrogen protection, extrude in 80～200 ℃ of frit reactions; granulation or directly through blowing; plastic uptake; injection moulding; calendering technology is processed into mutually deserved goods; the residence time of raw material in extrusion equipment is 3～30 minutes; when used aliphatic poly esterdiol when being a kind of; the proportioning of itself and hydroxyl-terminated polylactic acid is 1～10: 1～10 by weight; when used aliphatic poly esterdiol is two kinds; the proportioning of itself and hydroxyl-terminated polylactic acid is 1～10: 1～10: 1～10 by weight, and chainextender vulcabond consumption is 0.5～10% of hydroxyl-terminated polylactic acid and an aliphatic poly esterdiol gross weight.
The intrinsic viscosity of used hydroxyl-terminated polylactic acid is 0.05～0.5dL/g in the inventive method, gets by melt polymerization process, and its preparation method is seen document Kari Hiltunen, Mika
Jukka V.Macromolecules1996 (29): 8677～8682.
The intrinsic viscosity of used aliphatic poly junket glycol is 0.1～1.0dL/g in the inventive method, specifically can be at least a in polyalcohols acid esters glycol, the polylactone glycol.Wherein polyalcohols acid esters glycol is poly-acetate glycol ester glycol, poly-oxalic acid butanediol ester glycol, the polyethylene glycol succinate glycol, poly-succinic propylene glycol junket glycol, the poly butylene succinate glycol, oneself two ferment esterdiols of poly-succinic, the polyethylene glycol adipate glycol, the polypropylene adipate (PPA) glycol, the poly adipate succinic acid ester glycol, poly-hexanodioic acid hexylene glycol esterdiol, at least a in the poly butylene succinate copolymerization tetramethylene adipate glycol, preferred polyethylene glycol succinate glycol, the poly butylene succinate glycol, poly-hexanodioic acid hexylene glycol esterdiol, poly butylene succinate copolymerization tetramethylene adipate glycol.The preparation method of polyalcohols acid esters glycol sees document Chaoyi Ba, Jing Yang, and Qinghui Hao.Biomacromolecules 2003 (4): 1827～1834.At least a in poly-beta-butyrolactone glycol, poly-δ-Wu Neizhi glycol, the poly-epsilon-caprolactone glycol of polylactone glycol, its preparation method is seen document Schindler A, Hibionada M, Pitt CG.J Polym Sci, PolymChem Edi 1982 (20): 319～326.
Used chainextender vulcabond is any in tolylene diisocyanate, '-diphenylmethane diisocyanate, xylylene diisocyanate, dicyclohexyl methane diisocyanate, the hexamethylene diisocyanate in the inventive method.
Compared with the prior art the present invention has the following advantages:
1, be to adopt melt polymerization process to get owing to the present invention prepares the used hydroxyl-terminated polylactic acid prepolymer of multipolymer, thereby a series of problems of being brought of the ring-opening polymerization technology of having avoided prior art to adopt, make the products therefrom cost low, can expand the Application Areas of poly(lactic acid) thus.
2, because gained polylactic-acid block copolymer of the present invention is to adopt hydroxyl-terminated polylactic acid prepolymer and the preparation of aliphatic poly esterdiol, thereby the institute multipolymer that obtains not only cost is low, and can also improve the mechanical property of poly(lactic acid), make advantages such as it has good toughness simultaneously, tensile strength is big, tension fracture elongation rate is high, good processability, and lay a good foundation for it uses as the commodity polymer material.
3, because gained polylactic-acid block copolymer of the present invention adopts hydroxyl-terminated polylactic acid prepolymer and aliphatic poly esterdiol to prepare, thereby both can make institute's multipolymer that obtains faster than industrialized aliphatic polyester degradation speed, cost is lower, can make its toughness better than poly(lactic acid) again.
4, because the inventive method technology is simple, reaction conditions is easy to control, thereby is easy to realize industrialization, particularly adopts the reaction extrusion way, more can realize mass-producing, serialization production.
Embodiment
Also the invention will be further described to provide embodiment below.Be necessary to be pointed out that at this following examples can not be interpreted as limiting the scope of the invention; if the person skilled in the art in this field makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belong to protection domain of the present invention.
Embodiment 1
Intrinsic viscosity is respectively hydroxyl-terminated polylactic acid prepolymer and the polyethylene glycol oxalate glycol of 0.09dL/g and 0.12dL/g; by weight weighing in 1: 1 and place reaction flask; under nitrogen protection; be warmed up to 140 ℃ stir melting mixing evenly after; adding consumption again is the chainextender tolylene diisocyanate of prepolymer gross weight 8.9%, gets final product in 20 minutes 140 ℃ of reactions.
With obtained product, make solvent with trichloromethane, recording its intrinsic viscosity with Ubbelohde viscometer under 25 ℃ is 0.81dL/g; The film that thickness is 0.3mm is made in product hot pressing on 130 ℃ of vulcanizing presses, measured mechanical properties in films according to GB/T1040-92, the tensile strength of film is 20.35MPa, and elongation at break is 275%.
Embodiment 2
Intrinsic viscosity is respectively hydroxyl-terminated polylactic acid prepolymer and the poly-oxalic acid butanediol ester glycol of 0.13dL/g and 0.17dL/g; by weight weighing in 1: 1 and place reaction flask; under nitrogen protection; be warmed up to 160 ℃ stir melting mixing evenly after; adding consumption again is the chainextender hexamethylene diisocyanate of prepolymer gross weight 5.3%, gets final product in 30 minutes 160 ℃ of reactions.
With obtained product, recording its intrinsic viscosity by embodiment 1 listed method is 1.39dL/g; The tensile strength of film is 27.35MPa, and elongation at break is 473%.
Embodiment 3
Intrinsic viscosity is respectively hydroxyl-terminated polylactic acid prepolymer and the poly-hexanodioic acid hexylene glycol esterdiol of 0.16dL/g and 0.21dL/g; by weight weighing in 1: 1 and place reaction flask; under nitrogen protection; be warmed up to 160 ℃ stir melting mixing evenly after; adding consumption again is the chainextender tolylene diisocyanate of prepolymer gross weight 4.1%, gets final product in 45 minutes 160 ℃ of reactions.
With obtained product, recording its intrinsic viscosity by embodiment 1 listed method is 1.35dL/g; The tensile strength of film is 28.49MPa, and elongation at break is 642%.
Embodiment 4
Intrinsic viscosity is respectively hydroxyl-terminated polylactic acid prepolymer, the poly-epsilon-caprolactone two pure and mild poly-δ-Wu Neizhi glycol of 0.16dL/g, 0.22dL/g and 0.21dL/g; by weight weighing in 5: 1: 10 and place reaction flask; under nitrogen protection; be warmed up to 160 ℃ stir melting mixing evenly after; adding consumption again is the chainextender hexamethylene diisocyanate of prepolymer gross weight 4.0%, gets final product in 45 minutes 160 ℃ of reactions.
With obtained product, recording its intrinsic viscosity by embodiment 1 listed method is 1.34dL/g; The tensile strength of film is 27.43MPa, and elongation at break is 627%.
Embodiment 5
Intrinsic viscosity is respectively hydroxyl-terminated polylactic acid prepolymer and the poly-epsilon-caprolactone glycol of 0.16dL/g and 0.22dL/g; by weight weighing in 1: 4 and place reaction flask; under nitrogen protection; be warmed up to 160 ℃ stir melting mixing evenly after; adding consumption again is the chainextender dicyclohexyl methane diisocyanate of prepolymer gross weight 6.2%, gets final product in 60 minutes 160 ℃ of reactions.
With obtained product, recording its intrinsic viscosity by embodiment 1 listed method is 1.96dL/g; The tensile strength of film is 28.37MPa, and elongation at break is 735%.
Embodiment 6
Intrinsic viscosity is respectively hydroxyl-terminated polylactic acid prepolymer and the polyethylene glycol succinate glycol of 0.21dL/g and 0.28dL/g; by weight weighing in 1: 2 and place reaction flask; under nitrogen protection; be warmed up to 160 ℃ stir melting mixing evenly after; adding consumption again is the chainextender hexamethylene diisocyanate of prepolymer gross weight 2.8%, gets final product in 45 minutes 160 ℃ of reactions.
With obtained product, recording its intrinsic viscosity by embodiment 1 listed method is 1.65dL/g; The tensile strength of film is 32.47MPa, and elongation at break is 563%.
Embodiment 7
Intrinsic viscosity is respectively hydroxyl-terminated polylactic acid prepolymer and the poly-hexanodioic acid hexylene glycol esterdiol of 0.21dL/g and 0.28dL/g; by weight weighing in 10: 1 and place reaction flask; under nitrogen protection; be warmed up to 160 ℃ stir melting mixing evenly after; adding consumption again is the chainextender tolylene diisocyanate of prepolymer gross weight 2.3%, gets final product in 30 minutes 160 ℃ of reactions.
With obtained product, recording its intrinsic viscosity by embodiment 1 listed method is 0.89dL/g; The tensile strength of film is 39.47MPa, and elongation at break is 102%.
Embodiment 8
Intrinsic viscosity is respectively hydroxyl-terminated polylactic acid prepolymer and the poly butylene succinate glycol of 0.21dL/g and 0.35dL/g; by weight weighing in 1: 4 and place reaction flask; under nitrogen protection; be warmed up to 170 ℃ stir melting mixing evenly after; adding consumption again is the chainextender dicyclohexyl methane diisocyanate of prepolymer gross weight 3.4%, gets final product in 45 minutes 170 ℃ of reactions.
With obtained product, recording its intrinsic viscosity by embodiment 1 listed method is 1.83dL/g; The tensile strength of film is 31.35MPa, and elongation at break is 626%.
Embodiment 9
Intrinsic viscosity is respectively hydroxyl-terminated polylactic acid prepolymer and the poly butylene succinate copolymerization tetramethylene adipate glycol of 0.21dL/g and 0.35dL/g; by weight weighing in 7: 3 and place reaction flask; under nitrogen protection; be warmed up to 180 ℃ stir melting mixing evenly after; adding consumption again is the chainextender '-diphenylmethane diisocyanate of prepolymer gross weight 3.8%, gets final product in 20 minutes 180 ℃ of reactions.
With obtained product, recording its intrinsic viscosity by embodiment 1 listed method is 1.06dL/g; The tensile strength of film is 35.47MPa, and elongation at break is 427%.
Embodiment 10
Intrinsic viscosity is respectively hydroxyl-terminated polylactic acid prepolymer and the poly-hexanodioic acid hexylene glycol esterdiol of 0.27dL/g and 0.43dL/g; by weight weighing in 4: 1 and place reaction flask; under nitrogen protection; be warmed up to 170 ℃ stir melting mixing evenly after; adding consumption again is the chainextender hexamethylene diisocyanate of prepolymer gross weight 2.0%, gets final product in 30 minutes 170 ℃ of reactions.
With obtained product, recording its intrinsic viscosity by embodiment 1 listed method is 1.25dL/g; The tensile strength of film is 38.25MPa, and elongation at break is 315%.
Embodiment 11
Intrinsic viscosity is respectively hydroxyl-terminated polylactic acid prepolymer and the poly-hexanodioic acid hexylene glycol esterdiol of 0.35dL/g and 0.75dL/g; by weight weighing in 1: 10 and place reaction flask; under nitrogen protection; be warmed up to 180 ℃ stir melting mixing evenly after; adding consumption again is the chainextender xylylene diisocyanate of prepolymer gross weight 1.5%, gets final product in 90 minutes 180 ℃ of reactions.
With obtained product, recording its intrinsic viscosity by embodiment 1 listed method is 2.35dL/g; The tensile strength of film is 30.35MPa, and elongation at break is 725%.
Embodiment 12
Intrinsic viscosity is respectively hydroxyl-terminated polylactic acid prepolymer and the poly butylene succinate glycol of 0.47dL/g and 0.95dL/g; by weight weighing in 2: 1 and place reaction flask; under nitrogen protection; be warmed up to 180 ℃ stir melting mixing evenly after; adding consumption again is the chainextender xylylene vulcabond of prepolymer gross weight 2.2%, gets final product in 120 minutes 180 ℃ of reactions.
With obtained product, recording its intrinsic viscosity by embodiment 1 listed method is 1.47dL/g; The tensile strength of film is 35.35MPa, and elongation at break is 445%.
Embodiment 13
Intrinsic viscosity is respectively hydroxyl-terminated polylactic acid prepolymer and the poly-δ-Wu Neizhi glycol of 0.09dL/g and 0.12dL/g; by weight weighing in 2: 3; and be after the chainextender '-diphenylmethane diisocyanate of prepolymer gross weight 9.5% places mixer pre-mixing evenly with consumption; directly pass through charging machine; adding the twin screw extruder reaction under nitrogen protection extrudes; granulation or directly through blowing; plastic uptake; injection moulding; calendering technology is processed into corresponding goods; each section of twin screw extruder temperature is: 60 ℃ of feeding sections; 130 ℃ of melt zones; 100 ℃ of discharge ports, raw material is 5 minutes by the time of forcing machine.
With obtained product, recording its intrinsic viscosity by embodiment 1 listed method is 0.95dL/g; The tensile strength of film is 23.37MPa, and elongation at break is 427%.
Embodiment 14
Intrinsic viscosity is respectively 0.16dL/g; 0.21dL/g and the hydroxyl-terminated polylactic acid prepolymer of 0.21dL/g; poly butylene succinate two pure and mild polyethylene glycol succinate glycol; by weight weighing in 1: 2: 2; and be after the xylylene diisocyanate of prepolymer gross weight 4.5% places mixer pre-mixing evenly with consumption; directly pass through charging machine; adding the twin screw extruder reaction under nitrogen protection extrudes; granulation or directly through blowing; plastic uptake; injection moulding; calendering technology is processed into corresponding goods; each section of twin screw extruder temperature is: 60 ℃ of feeding sections; 150 ℃ of melt zones; 100 ℃ of discharge ports, raw material is 10 minutes by the time of forcing machine.
With obtained product, recording its intrinsic viscosity by embodiment 1 listed method is 1.57dL/g; The tensile strength of film is 29.33MPa, and elongation at break is 634%.
Embodiment 15
Intrinsic viscosity is respectively hydroxyl-terminated polylactic acid prepolymer and the poly butylene succinate glycol of 0.27dL/g and 0.43dL/g; by weight weighing in 3: 2; and be after the chainextender '-diphenylmethane diisocyanate of prepolymer gross weight 2.8% places mixer pre-mixing evenly with consumption; directly pass through charging machine; adding the twin screw extruder reaction under nitrogen protection extrudes; granulation or directly through blowing; plastic uptake; injection moulding; calendering technology is processed into corresponding goods; each section of twin screw extruder temperature is: 60 ℃ of feeding sections; 160 ℃ of melt zones; the temperature of discharge port is 100 ℃, and raw material is 10 minutes by the time of forcing machine.
With obtained product, recording its intrinsic viscosity by embodiment 1 listed method is 1.25dL/g; The tensile strength of film is 33.45MPa, and elongation at break is 524%.
Embodiment 16
Intrinsic viscosity is respectively hydroxyl-terminated polylactic acid prepolymer and the polyethylene glycol succinate glycol of 0.35dL/g and 0.75dL/g; by weight weighing in 3: 7; and be after the chainextender tolylene diisocyanate of prepolymer gross weight 1.0% places mixer pre-mixing evenly with consumption; directly pass through charging machine; adding the twin screw extruder reaction under nitrogen protection extrudes; granulation or directly through blowing; plastic uptake; injection moulding; calendering technology is processed into corresponding goods; each section of twin screw extruder temperature is: 60 ℃ of feeding sections; 170 ℃ of melt zones; 100 ℃ of discharge ports, raw material is 20 minutes by the time of forcing machine.
With obtained product, recording its intrinsic viscosity by embodiment 1 listed method is 1.44dL/g; The tensile strength of film is 28.28MPa, and elongation at break is 604%.
Embodiment 17
Intrinsic viscosity is respectively 0.47dL/g; 0.75dL/g and the hydroxyl-terminated polylactic acid prepolymer of 0.75dL/g; poly-hexanodioic acid hexylene glycol esterdiol and poly butylene succinate glycol; by weight weighing in 10: 5: 1; and be after the chainextender dicyclohexyl vulcabond of prepolymer gross weight 1.5% places mixer pre-mixing evenly with consumption; directly pass through charging machine; adding the twin screw extruder reaction under nitrogen protection extrudes; granulation or directly through blowing; plastic uptake; injection moulding; calendering technology is processed into corresponding goods; each section of twin screw extruder temperature is: 60 ℃ of feeding sections; 180 ℃ of melt zones; 100 ℃ of discharge ports, raw material is 20 minutes by the time of forcing machine.
With obtained product, recording its intrinsic viscosity by embodiment 1 listed method is 1.29dL/g; The tensile strength of film is 35.74MPa, and elongation at break is 515%.
Embodiment 18
Intrinsic viscosity is respectively 0.47dL/g; 0.94dL/g and the hydroxyl-terminated polylactic acid prepolymer of 0.95dL/g; poly-epsilon-caprolactone two pure and mild poly butylene succinate glycol; by weight weighing in 4: 1: 1; and be after the chainextender '-diphenylmethane diisocyanate of prepolymer gross weight 1.4% places mixer pre-mixing evenly with consumption; directly pass through charging machine; adding the twin screw extruder reaction under nitrogen protection extrudes; granulation or directly through blowing; plastic uptake; injection moulding; calendering technology is processed into corresponding goods; each section of twin screw extruder temperature is: 60 ℃ of feeding sections; 200 ℃ of melt zones; 100 ℃ of discharge ports, raw material is 30 minutes by the time of forcing machine.
With obtained product, recording its intrinsic viscosity by embodiment 1 listed method is 1.37dL/g; The tensile strength of film is 35.27MPa, and elongation at break is 475%.
Claims (6)
1, a kind of polylactic-acid block copolymer, it is characterized in that this multipolymer is that the poly(lactic acid) of 0.05～0.5dL/g and aliphatic poly esterdiol that intrinsic viscosity is 0.1～1.0dL/g get through the frit reaction preparation in the presence of the chainextender vulcabond by intrinsic viscosity, its repeating structure is as follows:
Or
Wherein PLA represents polylactic acid chain segment, APE
1, APE
2Represent two kinds of different aliphatic polyester segments, R represents the structure of hydrocarbyl portion in the chainextender vulcabond, this multipolymer is made solvent with trichloromethane, the intrinsic viscosity that records under 25 ℃ with Ubbelohde viscometer is 0.7～2.5dL/g, tensile strength and elongation at break are measured according to GB/T 1040-92 and are respectively 10～40MPa, 100～800%.
2; a kind of method for preparing the described segmented copolymer of claim 1; this method is to be that the hydroxyl-terminated polylactic acid of 0.05～0.5dL/g and aliphatic poly esterdiol that intrinsic viscosity is 0.1～1.0dL/g are as prepolymer with intrinsic viscosity; it is even to be warmed up to 130～200 ℃ of stirring melting mixing under protection of inert gas; add the chainextender vulcabond then 130～200 ℃ of reactions 3～120 minutes; or with hydroxyl-terminated polylactic acid; aliphatic poly esterdiol and chainextender vulcabond are together after the pre-mixing; under nitrogen protection, extrude in 80～200 ℃ of frit reactions; granulation or directly through blowing; plastic uptake; injection moulding; calendering technology is processed into corresponding articles; the residence time of raw material in extrusion equipment is 3～30 minutes; when used aliphatic poly esterdiol is two kinds; the proportioning of itself and hydroxyl-terminated polylactic acid is 1～10: 1～10: 1～10 by weight, and chainextender vulcabond consumption is 0.5～10% of hydroxyl-terminated polylactic acid and an aliphatic poly esterdiol gross weight.
3, the method for preparing segmented copolymer according to claim 2 is characterized in that used aliphatic poly esterdiol is polyalcohols acid esters two pure and mild polylactone glycol.
4, the method for preparing segmented copolymer according to claim 3 is characterized in that used polyalcohols acid esters glycol is at least a in polyethylene glycol oxalate glycol, poly-oxalic acid butanediol ester glycol, polyethylene glycol succinate glycol, poly-succinic propylene glycol ester glycol, poly butylene succinate glycol, poly-succinic hexylene glycol esterdiol, polyethylene glycol adipate glycol, polypropylene adipate (PPA) glycol, poly adipate succinic acid ester glycol, poly-hexanodioic acid hexylene glycol esterdiol, the poly butylene succinate copolymerization tetramethylene adipate glycol; At least a in poly-beta-butyrolactone glycol, poly-δ-Wu Neizhi glycol, the poly-epsilon-caprolactone glycol of polylactone glycol.
5,, it is characterized in that used chainextender vulcabond is any in tolylene diisocyanate, '-diphenylmethane diisocyanate, xylylene diisocyanate, dicyclohexyl methane diisocyanate, the hexamethylene diisocyanate according to claim 2 or the 3 described methods that prepare segmented copolymer.
6, the method for preparing segmented copolymer according to claim 4 is characterized in that used chainextender vulcabond is any in tolylene diisocyanate, '-diphenylmethane diisocyanate, xylylene diisocyanate, dicyclohexyl methane diisocyanate, the hexamethylene diisocyanate.
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| CN101914281A (en) * | 2010-08-03 | 2010-12-15 | 营口巨成教学科技开发有限公司 | Thermoplastic elastomer composition |
| US9102782B2 (en) | 2011-08-12 | 2015-08-11 | China Petroleum & Chemical Corporation | Transparent copolyester, preparing method thereof and articles made from the same |
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