CN102838734B - Polylactic acid block polymer and preparation method thereof - Google Patents
Polylactic acid block polymer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polylactic acid block polymer and a preparation method thereof. The preparation method comprises the following steps: mixing poly(adipic acid-terephthalic acid)butanediol copolyester, lactide and a first catalyst, and heating to a molten state to react, thereby obtaining the polylactic acid block polymer disclosed as Formula (I). Compared with the polymer obtained by the PLA-PBAT chain extension reaction initiated by diisocyanate in the prior art, the invention uses the molten-state poly(adipic acid-terephthalic acid)butanediol copolyester as the reactant to directly initiate the ring-opening polymerization of lactide, and the polymerization method is mass polymerization without adding the chain extender diisocyanate or any organic solvent, thereby avoiding jeopardizing the human body and environment; the raw materials can be mixed and heated to react to obtain the polylactic acid block polymer, so that the preparation method is simpler and lowers the preparation cost; and the polylactic acid block polymer provided by the invention has definite structure and narrow molecular weight distribution.
Description
Technical field
Polymeric material field of the present invention, relates in particular to a kind of polylactic-acid block copolymer and preparation method thereof.
Background technology
Plastics are absolutely necessary in people's life, but traditional plastics are general, above the even longer time of a century could be degradable, caused serious " white pollution "; Traditional plastic raw materials all derives from the Nonrenewable resources such as oil simultaneously, and the plastics industry traditional along with the exhaustion of petrochemical industry resource is also on the hazard.Therefore the eco-friendly biodegradable polymkeric substance petroleum replacing base plastic prod of Devoting Major Efforts To Developing, has become the focus that current research is developed.
Wherein, poly(lactic acid) (PLA) is very important a kind of bio-degradable plastics, that to take the lactic acid that agricultural-food corn refines be monomer, Biodegradable macromolecular material through chemosynthesis, there is nontoxic, nonirritant, good biocompatibility, intensity is high and the feature such as biodegradable and absorption, in wrapping material, biological medicine and pharmaceutical industry, have a wide range of applications.And the degradation speed of poly(lactic acid) is very fast, mix with microorganism and compound organic waste materials, can within some months, resolve into CO
2and H
2o.Therefore strengthen polylactic acid-based product development and application, can solve " white pollution " that perplex for a long time environment protection, and have great importance to realizing Sustainable development.
But because long-chain branch in polylactic acid molecule chain is few, shortcomings such as making it have that melt strength is low, strain hardening is not enough, toughness is poor, lack flexibility and elasticity, tear strength is low, the polymkeric substance hard and crisp for this class of poly(lactic acid) in thermoforming, melt strength is low, moulding process can only be carried out in narrow temperature range, so its application is subject to certain restrictions.And, owing to not containing the functional group with reactive behavior in the molecular chain of poly(lactic acid), be difficult for introducing long-chain branch, therefore need to find suitable PLA modified method, under the condition that does not affect the performances such as PLA biological degradability, biocompatibility, intensity, improve its shortcoming.
Poly-(hexanodioic acid-terephthalic acid)-butanediol copolyester (PBAT) is by terephthalic acid (PTA), hexanodioic acid (AA) and 1,4-butyleneglycol (1, a kind of long-chain fat family-aromatic copolyester macromolecular material that carboxylate condensation 3-BD) obtains, it combines the degradability of aliphatic polyester and mechanics and the thermal property of aromatic polyester excellence, compare with PLA, there is biodegradation rate and good snappiness faster.Research shows, after PBAT and PLA blend, the storage modulus of blend and viscosity improve gradually with the increase of PBAT content, and the elongation at break of blend and shock strength are all improved.But the consistency of PLA and PBAT is poor, the product performance that physical blending obtains are unstable.
At present, for the problem of physical blending, Yuan Hua etc. have proposed to add chainextender hexamethylene diisocyanate, utilize the chain extending reaction between PLA and PBAT, in PLA molecular chain, introduce methene chain and phenyl ring unit, the crosslinked polymkeric substance that obtains.The elongation at break of this polymkeric substance can reach 364.35%, but the toxicity of vulcabond has limited the range of application of this product, and its molecular weight distribution obtaining is wider.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of polylactic-acid block copolymer and preparation method thereof, and the method is nontoxic.
The invention provides a kind of polylactic-acid block copolymer, as shown in the formula (I):
Wherein, p=20 ~ 1400, n=5 ~ 200, m=5 ~ 200.
The preparation method who the invention provides a kind of polylactic-acid block copolymer, comprises the following steps:
To gather (hexanodioic acid-terephthalic acid) butanediol copolyester, rac-Lactide and the first catalyst mix, be heated to molten state, after reacting, obtain the polylactic-acid block copolymer of formula (I) structure;
Wherein, p=20 ~ 1400, n=5 ~ 200, m=5 ~ 200.
Preferably, the mass ratio of described rac-Lactide and poly-(hexanodioic acid-terephthalic acid) butanediol copolyester is (1:9) ~ (9:1).
Preferably, the quality of described the first catalyzer is 0.01% ~ 1% of rac-Lactide quality.
Preferably, described the first catalyzer is selected from one or more in aluminum isopropylate, divinyl zinc, tin protochloride and stannous octoate.
Preferably, the temperature of reaction of described reaction is 80 ℃ ~ 180 ℃, and the reaction times is 3 ~ 50h.
Preferably, described poly-(hexanodioic acid-terephthalic acid) butanediol copolyester is prepared according to following steps:
By terephthaldehyde's acid source, hexanodioic acid, butyleneglycol and the second catalyst mix, carry out successively esterification and polycondensation, gathered (hexanodioic acid-terephthalic acid) butanediol copolyester, described terephthaldehyde's acid source is terephthalic acid and/or terephthalic acid ester derivative.
Preferably, described terephthaldehyde acid derivative is selected from one or more in dimethyl terephthalate (DMT), diethyl terephthalate, dioctyl terephthalate and ethylene glycol terephthalate.
Preferably, the quality of described the second catalyzer is 0.01% ~ 1% of terephthaldehyde's acid source and hexanodioic acid total mass.
Preferably, described the second catalyzer is selected from one or more in tetrabutyl titanate, tin protochloride, isopropyl titanate, stannous octoate, zinc acetate and tosic acid.
The invention provides a kind of polylactic-acid block copolymer and preparation method thereof, the method will be gathered (hexanodioic acid-terephthalic acid) butanediol copolyester, rac-Lactide and the first catalyst mix, be heated to molten state, after reacting, obtain the polylactic-acid block copolymer of formula (I) structure.And the chain extending reaction that prior art vulcabond causes between PLA and PBAT obtains polymer phase ratio, the present invention directly causes with poly-(hexanodioic acid-terephthalic acid) butanediol copolyester of molten state the polylactic-acid block copolymer that rac-Lactide ring-opening polymerization obtains formula (I) structure.First, the present invention directly causes rac-Lactide ring-opening polymerization with poly-(hexanodioic acid-terephthalic acid) butanediol copolyester of molten state as reactant, its polymerization process is mass polymerization, in polymerization process, do not add chainextender vulcabond and any organic solvent, the harm of having avoided vulcabond and organic solvent to bring human body and environment; Secondly, can obtain the polylactic-acid block copolymer of formula (I) structure after raw material Hybrid Heating reaction of the present invention, preparation method is simpler, and condition is gentleer, has reduced preparation cost; Again, the polylactic-acid block copolymer structure of the formula that the present invention prepares (I) structure is clear and definite, the molecular weight of copolymer narrow distribution obtaining.
Experimental result shows, the polylactic-acid block copolymer molecular weight distribution of the formula that the present invention prepares (I) structure is 1.8 left and right, and fusing point is 172 ℃, and heat decomposition temperature is 275 ℃.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of poly-(hexanodioic acid-terephthalic acid) butanediol copolyester of preparation in the embodiment of the present invention 1;
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the polylactic-acid block copolymer of formula (I) structure of preparation in the embodiment of the present invention 1;
Fig. 3 is the stress-strain curve diagram of the polylactic-acid block copolymer of formula (I) structure of preparation in the embodiment of the present invention 1.
Embodiment
The invention provides a kind of polylactic-acid block copolymer, as shown in the formula (I):
Wherein, p==20 ~ 1400, are preferably 100 ~ 1200, and more preferably 200 ~ 1000, then be preferably 400 ~ 800, n=5 ~ 200, be preferably 15 ~ 150, more preferably 50 ~ 100, m=5 ~ 200, are preferably 20 ~ 160, and more preferably 40 ~ 120, then be preferably 60 ~ 100.
The relative number average molecular weight of the polylactic-acid block copolymer of described formula (I) structure is 60 ~ 120kg/mol, be preferably 70 ~ 110kg/mol, 80 ~ 100kg/mol more preferably, fusing point is 165 ℃ ~ 178 ℃, be preferably 170 ℃ ~ 175 ℃, second-order transition temperature is 58 ℃ ~ 63 ℃, is preferably 60 ℃ ~ 63 ℃, heat decomposition temperature is 274 ℃ ~ 276 ℃, is preferably 275 ℃.
The present invention also provides a kind of preparation method of polylactic-acid block copolymer, comprise the following steps: will gather (hexanodioic acid-terephthalic acid) butanediol copolyester, rac-Lactide and the first catalyst mix, be heated to molten state, after reacting, obtain the polylactic-acid block copolymer of formula (I) structure.The polylactic-acid block copolymer of described formula (I) structure is same as above, does not repeat them here.
The mass ratio of rac-Lactide described in the present invention and poly-(hexanodioic acid-terephthalic acid) butanediol copolyester is (1:9) ~ (9:1), be preferably (1:1) ~ (6:1), more preferably (1.5:1) ~ (4:1), then be preferably (1.5:1) ~ (3:1).Poly-(hexanodioic acid-terephthalic acid) butanediol copolyester has good snappiness, causes rac-Lactide ring-opening polymerization formation segmented copolymer and can make up poly(lactic acid) shortage flexibility and elastic shortcoming.
The quality of described the first catalyzer is 0.01% ~ 1% of rac-Lactide massfraction, is preferably 0.04% ~ 0.5%, more preferably 0.05% ~ 0.3%, then be preferably 0.08% ~ 0.2%.Described the first catalyzer is the catalyzer of rac-Lactide ring-opening polymerization, catalyzer for ring-opening polymerization well known to those skilled in the art, described the first catalyzer is preferably selected from one or more in aluminum isopropylate, divinyl zinc, tin protochloride and stannous octoate in the present invention, more preferably tin protochloride or stannous octoate, then be preferably stannous octoate.
According to the present invention, described reaction is rac-Lactide ring-opening polymerization, the temperature of reaction of described reaction is 80 ℃ ~ 180 ℃, be preferably 90 ℃ ~ 160 ℃, more preferably 100 ℃ ~ 140 ℃, rac-Lactide is molten state, and polymerization process is mass polymerization, therefore without adding vulcabond and any organic reagent, nontoxic.The reaction times of described reaction is 3 ~ 50h, is preferably 5 ~ 40h, 7 ~ 30h more preferably, then be preferably 9 ~ 20h.
After rac-Lactide ring-opening polymerization finishes, preferably pass into nitrogen and carry out devolatilization, remove unreacted monomer, extruding pelletization then, obtains the polylactic-acid block copolymer of formula (I) structure.The method of described extruding pelletization there is no special restriction, is method well known to those skilled in the art.
According to the present invention, described poly-(hexanodioic acid-terephthalic acid) butanediol copolyester is preferably prepared according to following steps: by terephthaldehyde's acid source, hexanodioic acid, butyleneglycol and the second catalyst mix, carry out successively esterification and polycondensation, gathered (hexanodioic acid-terephthalic acid) butanediol copolyester.Described terephthaldehyde's acid source is terephthalic acid and/or terephthalic acid ester derivative.
Relationship between quality between raw material terephthaldehyde acid source, hexanodioic acid and the butyleneglycol of described poly-(hexanodioic acid-terephthalic acid) butanediol copolyester meets the relationship between quality of general esterification, the integral molar quantity of terephthaldehyde's acid source and hexanodioic acid is less than the molar weight of butyleneglycol, and the pass between terephthaldehyde's acid source and oxalic acid is that the ratio of its molar weight is (10:90) ~ (90:10).
Wherein, described terephthalic acid ester derivative is selected from one or more in dimethyl terephthalate (DMT), diethyl terephthalate, dioctyl terephthalate and ethylene glycol terephthalate.
The quality of described the second catalyzer is 0.01% ~ 1% of terephthaldehyde's acid source and hexanodioic acid total mass, is preferably 0.04% ~ 0.6%, more preferably 0.05% ~ 0.4%, then be preferably 0.06% ~ 0.2%.Described the second catalyzer is well known to those skilled in the art, common catalyzer in poly-(hexanodioic acid-terephthalic acid) butanediol copolyester is synthetic, be preferably and be selected from one or more in tetrabutyl titanate, tin protochloride, isopropyl titanate, stannous octoate, zinc acetate and tosic acid, be preferably and be selected from one or more in tetrabutyl titanate, tin protochloride, isopropyl titanate and stannous octoate, more preferably tetrabutyl titanate.
Esterification described in the present invention and polycondensation are common reaction during poly-(hexanodioic acid-terephthalic acid) butanediol copolyester well known to those skilled in the art synthesizes, and there is no special restriction.
In the present invention, esterification is preferably under the condition of normal pressure protection of inert gas and carries out, and esterification reaction temperature is 140 ℃ ~ 230 ℃, is preferably 140 ℃ ~ 200 ℃, more preferably 140 ℃ ~ 180 ℃; The reaction times of esterification, for the water producing in reaction reaches theoretical aquifer yield, is preferably 1 ~ 8h, 2 ~ 6h more preferably, then be preferably 4 ~ 5h.Described inert protective gas is rare gas element well known to those skilled in the art, is preferably nitrogen or argon gas.
In the present invention, polycondensation is preferably carried out under vacuum low-pressure, and the pressure of polycondensation is 10 ~ 250Pa, is preferably 50 ~ 200Pa, more preferably 80 ~ 150Pa; The temperature of reaction of described polycondensation is 210 ℃ ~ 280 ℃, is preferably 210 ℃ ~ 260 ℃, more preferably 210 ℃ ~ 240 ℃; The reaction times of described polycondensation, for stirring voltage is increased to definite value, is preferably 80 ~ 220V, and 80 ~ 180V more preferably, and record agitator revolution treats that stirring velocity is stable, and reaction finishes, and is preferably 2 ~ 48h, 6 ~ 40h more preferably, then be preferably 10 ~ 30h.
According to the present invention, being preferably one kettle way reacts, poly-(hexanodioic acid-terephthalic acid) butanediol copolyester and polylactic-acid block copolymer are synthetic, carry out successively, figure below is the response path of the polylactic-acid block copolymer of formula (I) structure, wherein take phthalic acid, hexanodioic acid and butyleneglycol to gather as synthetic (hexanodioic acid-terephthalic acid) butanediol copolyester raw material used.After poly-(hexanodioic acid-terephthalic acid) butanediol copolyester is synthetic, without dissolving the steps such as sedimentation, carry out purifying, directly cool the temperature to 80 ℃ ~ 180 ℃, be preferably 90 ℃ ~ 160 ℃, more preferably 100 ℃ ~ 140 ℃, add rac-Lactide to carry out ring-opening polymerization, now poly-(hexanodioic acid-terephthalic acid) butanediol copolyester and rac-Lactide are molten state, described ring-opening polymerization is mass polymerization, poly-(hexanodioic acid-terephthalic acid) butanediol copolyester of molten state directly causes rac-Lactide ring-opening polymerization as reactant, in polymerization process without adding chainextender vulcabond and any organic solvent, the harm of having avoided vulcabond and organic solvent to bring human body and environment, one kettle way reacts, and omitted the purification steps such as middle dissolving sedimentation, and condition is gentleer, has reduced preparation cost.
Wherein, wherein, p=20 ~ 1400, are preferably 100 ~ 1200, and more preferably 200 ~ 1000, then be preferably 400 ~ 800, n=5 ~ 200, be preferably 15 ~ 150, more preferably 50 ~ 100, m=5 ~ 200, are preferably 20 ~ 160, and more preferably 40 ~ 120, then be preferably 60 ~ 100.Y is the molar weight of butyleneglycol, according to the demand of esterification well known to those skilled in the art, adds, and there is no special restriction.
Result shows, the present invention adopts poly-(hexanodioic acid-terephthalic acid) butanediol copolyester of molten state directly to cause rac-Lactide ring-opening polymerization as reactant, and the polylactic-acid block copolymer structure obtaining is clear and definite, and molecular weight distribution is narrower.
In order to further illustrate the present invention, below in conjunction with embodiment, the preparation method of a kind of polylactic-acid block copolymer provided by the invention is described in detail.
In following examples, reagent used is commercially available.
Embodiment 1
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 90g butyleneglycol and 0.1g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 140 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 210 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value, obtains; Reduce temperature to 120 ℃, the rac-Lactide and the 0.7g stannous octoate that add 700g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 100.0kg/mol, relative molecular weight is distributed as 1.75, and relative molecular weight is distributed as the unimodal of symmetry.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 1, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.2 ℃, and heat decomposition temperature is 275 ℃.
Utilize nucleus magnetic resonance respectively poly-(hexanodioic acid-terephthalic acid) butanediol copolyester obtaining in embodiment 1 and the polylactic-acid block copolymer of formula (I) structure to be analyzed, obtain the hydrogen nuclear magnetic resonance spectrogram of two chemicals, as depicted in figs. 1 and 2, Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of poly-(hexanodioic acid-terephthalic acid) butanediol copolyester, Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the polylactic-acid block copolymer of formula (I) structure, a in figure, b, c, d, e, f and g are respectively the displacement of different hydro in polymkeric substance.
According to GB/T 1040-92, the polylactic-acid block copolymer of the formula obtaining in embodiment 1 (I) structure is carried out to tensile property test, obtain its stress-strain curve diagram, as shown in Figure 3.The elongation at break of the polylactic-acid block copolymer that the present invention prepares is as shown in Figure 3 compared with poly(lactic acid), is enhanced, and toughness increases.
Embodiment 2
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 90g butyleneglycol and 0.1g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 140 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 210 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.46g stannous octoate that add 460g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 70.0kg/mol, relative molecular weight is distributed as 1.78, and relative molecular weight is distributed as the unimodal of symmetry.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 2, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.0 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 3
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 90g butyleneglycol and 0.1g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 180 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 210 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.7g stannous octoate that add 700g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 95.0kg/mol, relative molecular weight is distributed as 1.79, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 3, obtaining its fusing point is 172 ℃, and second-order transition temperature is 61.9 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 4
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 90g butyleneglycol and 0.1g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 180 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 210 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.46g stannous octoate that add 460g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 65.0kg/mol, relative molecular weight is distributed as 1.76, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 4, obtaining its fusing point is 172 ℃, and second-order transition temperature is 61.5 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 5
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 90g butyleneglycol and 0.1g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 140 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 240 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.7g stannous octoate that add 700g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 110.0kg/mol, relative molecular weight is distributed as 1.82, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 5, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.3 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 6
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 90g butyleneglycol and 0.1g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 140 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 240 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.46g stannous octoate that add 460g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 73.0kg/mol, relative molecular weight is distributed as 1.85, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 6, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.2 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 7
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 90g butyleneglycol and 0.1g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 180 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 240 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.7g stannous octoate that add 700g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 105.0kg/mol, relative molecular weight is distributed as 1.77, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 7, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.3 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 8
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 90g butyleneglycol and 0.1g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 180 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 240 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.46g stannous octoate that add 460g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 72.0kg/mol, relative molecular weight is distributed as 1.72, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 8, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.0 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 9
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 90g butyleneglycol and 0.2g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 140 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 210 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.7g stannous octoate that add 700g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 105.0kg/mol, relative molecular weight is distributed as 1.73, and relative molecular weight is distributed as the unimodal of symmetry.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 9, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.4 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 10
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 90g butyleneglycol and 0.2g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 140 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 210 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.46g stannous octoate that add 400g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 72.0kg/mol, relative molecular weight is distributed as 1.78, and relative molecular weight is distributed as the unimodal of symmetry.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 10, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.1 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 11
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 90g butyleneglycol and 0.2g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 180 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 210 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.66g stannous octoate that add 700g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 100.0kg/mol, relative molecular weight is distributed as 1.82, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 11, obtaining its fusing point is 172 ℃, and second-order transition temperature is 61.9 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 12
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 90g butyleneglycol and 0.2g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 180 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 210 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.46g stannous octoate that add 460g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 70.0kg/mol, relative molecular weight is distributed as 1.78, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 12, obtaining its fusing point is 172 ℃, and second-order transition temperature is 61.5 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 13
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 90g butyleneglycol and 0.1g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 140 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 240 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.7g stannous octoate that add 700g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 103.0kg/mol, relative molecular weight is distributed as 1.87, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 13, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.2 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 14
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 90g butyleneglycol and 0.2g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 140 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 240 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.45g stannous octoate that add 460g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 74.0kg/mol, relative molecular weight is distributed as 1.81, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 14, obtaining its fusing point is 172 ℃, and second-order transition temperature is 61.7 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 15
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 90g butyleneglycol and 0.2g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 180 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 240 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.7g stannous octoate that add 700g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 101.0kg/mol, relative molecular weight is distributed as 1.82, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 15, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.1 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 16
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 90g butyleneglycol and 0.2g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 180 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 240 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.46g stannous octoate that add 460g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 73.0kg/mol, relative molecular weight is distributed as 1.72, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 16, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.0 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 17
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 135g butyleneglycol and 0.1g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 140 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 210 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.7g stannous octoate that add 700g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 105.0kg/mol, relative molecular weight is distributed as 1.79, and relative molecular weight is distributed as the unimodal of symmetry.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 17, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.6 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 18
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 135g butyleneglycol and 0.1g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 140 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 210 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.46g stannous octoate that add 460g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 71.0kg/mol, relative molecular weight is distributed as 1.83, and relative molecular weight is distributed as the unimodal of symmetry.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 18, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.1 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 19
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 135g butyleneglycol and 0.1g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 180 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 210 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.7g stannous octoate that add 700g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 97.0kg/mol, relative molecular weight is distributed as 1.79, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 19, obtaining its fusing point is 172 ℃, and second-order transition temperature is 61.7 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 20
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 135g butyleneglycol and 0.1g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 180 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 210 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.46g stannous octoate that add 460g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 68.0kg/mol, relative molecular weight is distributed as 1.76, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 20, obtaining its fusing point is 172 ℃, and second-order transition temperature is 61.5 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 21
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 135g butyleneglycol and 0.1g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 140 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 240 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.7g stannous octoate that add 700g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 112.0kg/mol, relative molecular weight is distributed as 1.85, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 21, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.5 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 22
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 135g butyleneglycol and 0.1g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 140 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 240 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.46g stannous octoate that add 460g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 77.0kg/mol, relative molecular weight is distributed as 1.85, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 22, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.2 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 23
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 135g butyleneglycol and 0.1g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 180 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 240 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.7g stannous octoate that add 700g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 107.0kg/mol, relative molecular weight is distributed as 1.77, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 23, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.3 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 24
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 135g butyleneglycol and 0.1g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 180 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 240 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.46g stannous octoate that add 460g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 75.0kg/mol, relative molecular weight is distributed as 1.72, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 24, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.1 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 25
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 135g butyleneglycol and 0.2g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 140 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 210 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.7g stannous octoate that add 700g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 102.0kg/mol, relative molecular weight is distributed as 1.75, and relative molecular weight is distributed as the unimodal of symmetry.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 25, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.1 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 26
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 135g butyleneglycol and 0.2g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 140 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 210 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.46g stannous octoate that add 460g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 73.0kg/mol, relative molecular weight is distributed as 1.78, and relative molecular weight is distributed as the unimodal of symmetry.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 26, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.1 ℃, and heat decomposition temperature is 273 ℃.
Embodiment 27
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 135g butyleneglycol and 0.2g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 180 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 210 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.66g stannous octoate that add 700g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 101.0kg/mol, relative molecular weight is distributed as 1.84, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 27, obtaining its fusing point is 172 ℃, and second-order transition temperature is 61.9 ℃, and heat decomposition temperature is 272 ℃.
Embodiment 28
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 135g butyleneglycol and 0.2g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 180 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 210 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.46g stannous octoate that add 460g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 70.5kg/mol, relative molecular weight is distributed as 1.78, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 28, obtaining its fusing point is 172 ℃, and second-order transition temperature is 61.5 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 29
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 135g butyleneglycol and 0.1g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 140 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 240 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.7g stannous octoate that add 700g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 112.0kg/mol, relative molecular weight is distributed as 1.87, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 29, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.6 ℃, and heat decomposition temperature is 277 ℃.
Embodiment 30
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 135g butyleneglycol and 0.2g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 140 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 240 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.45g stannous octoate that add 460g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 77.0kg/mol, relative molecular weight is distributed as 1.82, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 30, obtaining its fusing point is 172 ℃, and second-order transition temperature is 61.9 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 31
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 135g butyleneglycol and 0.2g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 180 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 240 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.7g stannous octoate that add 700g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 115.0kg/mol, relative molecular weight is distributed as 1.78, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 31, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.5 ℃, and heat decomposition temperature is 275 ℃.
Embodiment 32
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 135g butyleneglycol and 0.2g tetrabutyl titanate are added to in churned mechanically reactor, under normal pressure, be warming up to 180 ℃, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Then be warming up to 240 ℃, decompression step by step to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, records agitator revolution, to stirring revolution, no longer reduces and reaches definite value; Reduce temperature to 120 ℃, the rac-Lactide and the 0.46g stannous octoate that add 460g to be dried, reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains the polylactic-acid block copolymer of formula (I) structure, and number average mol weight is 79.0kg/mol, relative molecular weight is distributed as 1.76, and relative molecular weight is distributed as narrower peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in embodiment 32, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.1 ℃, and heat decomposition temperature is 275 ℃.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (9)
1. a preparation method for polylactic-acid block copolymer, is characterized in that, comprises the following steps:
To gather (hexanodioic acid-terephthalic acid) butanediol copolyester, rac-Lactide and the first catalyst mix, be heated to molten state, after reacting, obtain the polylactic-acid block copolymer of formula (I) structure;
Wherein, p=20～1400, n=5～200, m=5～200.
2. preparation method according to claim 1, is characterized in that, the mass ratio of described rac-Lactide and poly-(hexanodioic acid-terephthalic acid) butanediol copolyester is (1:9)～(9:1).
3. preparation method according to claim 1, is characterized in that, the quality of described the first catalyzer is 0.01%～1% of rac-Lactide quality.
4. preparation method according to claim 1, is characterized in that, described the first catalyzer is selected from one or more in aluminum isopropylate, divinyl zinc, tin protochloride and stannous octoate.
5. preparation method according to claim 1, is characterized in that, the temperature of reaction of described reaction is 80 ℃～180 ℃, and the reaction times is 3～50h.
6. preparation method according to claim 1, is characterized in that, described poly-(hexanodioic acid-terephthalic acid) butanediol copolyester is prepared according to following steps:
By terephthaldehyde's acid source, hexanodioic acid, butyleneglycol and the second catalyst mix, carry out successively esterification and polycondensation, gathered (hexanodioic acid-terephthalic acid) butanediol copolyester, described terephthaldehyde's acid source is terephthalic acid and/or terephthalic acid ester derivative.
7. preparation method according to claim 6, is characterized in that, described terephthaldehyde acid derivative is selected from one or more in dimethyl terephthalate (DMT), diethyl terephthalate, dioctyl terephthalate and ethylene glycol terephthalate.
8. preparation method according to claim 6, is characterized in that, the quality of described the second catalyzer is 0.01%～1% of terephthaldehyde's acid source and hexanodioic acid total mass.
9. preparation method according to claim 6, is characterized in that, described the second catalyzer is selected from one or more in tetrabutyl titanate, tin protochloride, isopropyl titanate, stannous octoate, zinc acetate and tosic acid.
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| CN104211929B (en) * | 2014-08-06 | 2016-01-13 | 中国科学院长春应用化学研究所 | A kind of organic zinc composition catalyst and method for making thereof and application |
| CN105440605B (en) * | 2014-08-29 | 2018-01-12 | 中国科学院长春应用化学研究所 | A kind of polylactic resin |
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| CN101338025B (en) * | 2008-08-12 | 2011-04-27 | 四川大学 | Polylactic acid/polyethylene terephthalate multi-block copolymer, method for preparing same and uses |
| CN102241810B (en) * | 2011-05-12 | 2012-11-28 | 中国科学院宁波材料技术与工程研究所 | Polylactic acid block copolymer and preparation method thereof |
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