CN102786672B - Preparation method of polylactic acid segmented copolymer - Google Patents
Preparation method of polylactic acid segmented copolymer Download PDFInfo
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Abstract
The invention provides a preparation method of a polylactic acid segmented copolymer. The preparation method includes: allowing succinic acid and butanediol to react under action of a first catalyst to obtain poly(butylene succinate) in a molten condition; and allowing the poly(butylene succinate) and lactide to react under a second catalyst to obtain the polylactic acid segmented copolymer. Compared with the prior art, a bulk polymerization method is used to synthesize the polylactic acid segmented copolymer, the poly(butylene succinate) in the molten condition is used to initiate ring opening polymerization of the lactide, no organic solvent is needed, and harm to human body and environment caused by the organic solvent is avoided; the poly(butylene succinate) in the molten condition can be directly used to initiate ring opening polymerization of the lactide without purification by dissolving and sediment, the poly(butylene succinate) in the molten condition is free of water, no dewatering and drying are needed, preparation process is simplified, and production cost is lowered.
Description
Technical field
The invention belongs to polymeric material field, relate in particular to a kind of preparation method of polylactic-acid block copolymer.
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.
At present, about the research of PLA modification, there are reports, publication number is the production method that the Chinese patent of CN101328307A discloses a kind of polylactic acid plasticize product, the polylactic acid and polyethylene butanediol succinate segmented copolymer and the polylactic acid blend that by rac-Lactide ring-opening polymerization, obtain, make polylactic acid plasticize product, this product has higher tensile modulus and lower water vapor transmission rate (WVTR), but the method complex process that synthetic segmented copolymer is used, condition is harsh, and cost is higher; Publication number is that the Chinese patent of CN101935390A discloses polylactic acid toughening modifier and preparation method thereof, its terminal hydroxy group that adopts solvent method to pass through poly butylene succinate causes rac-Lactide ring-opening polymerization, through purifying, obtain polylactic acid and polyethylene butanediol succinate segmented copolymer, the method can be carried out under lower temperature and normal pressure, but need absolute anhydrous environment, poly butylene succinate need be through dewatering finish-drying, and the organic solvent adding is volatile, environment and human body are worked the mischief.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method of polylactic-acid block copolymer, and the method is nontoxic and technique is simple.
The preparation method who the invention provides a kind of polylactic-acid block copolymer, comprises the following steps:
A) succinic acid and butyleneglycol are reacted under the effect of the first catalyzer, obtain the poly butylene succinate of molten state;
B) poly butylene succinate of described molten state is reacted under the effect of the second catalyzer with rac-Lactide, obtain polylactic-acid block copolymer.
Preferably, described the first catalyzer is one or more in tetrabutyl titanate, tin protochloride, isopropyl titanate, stannous octoate, zinc acetate and tosic acid.
Preferably, the mass ratio of described the first catalyzer and succinic acid is (0.01 ~ 1): 100.
Preferably, the mass ratio of described rac-Lactide and poly butylene succinate is (1 ~ 81): 9.
Preferably, the mass ratio of described the second catalyzer and rac-Lactide is (0.01 ~ 1): 100.
Preferably, described the second catalyzer is aluminum isopropylate, divinyl zinc, tin protochloride or stannous octoate.
Preferably, the temperature of reaction of reacting in described step B is 100 ℃ ~ 180 ℃, and the reaction times is 5 ~ 48h.
Preferably, described steps A is specially:
Under the condition of protection of inert gas, succinic acid and butyleneglycol are carried out to esterification under the effect of the first catalyzer, after vacuumizing, carry out polycondensation, obtain poly butylene succinate.
Preferably, the temperature of reaction of described esterification is 130 ℃ ~ 230 ℃, and the reaction times is 1 ~ 8h.
Preferably, the temperature of reaction of described polycondensation is 210 ℃ ~ 270 ℃, and the reaction times is 2 ~ 24h, and reaction pressure is 10 ~ 300Pa.
The invention provides a kind of preparation method of polylactic-acid block copolymer, the method is reacted succinic acid and butyleneglycol under the effect of the first catalyzer, obtains the poly butylene succinate of molten state; Further react under the effect of the second catalyzer with rac-Lactide, obtain polylactic-acid block copolymer.Compare with prior art solvent method synthesizing polylactic acid segmented copolymer, first, the present invention adopts the method synthesizing polylactic acid segmented copolymer of mass polymerization, the poly butylene succinate of molten state causes rac-Lactide ring-opening polymerization as reactant, therefore in polymerization process without adding organic solvent, the harm of avoiding organic solvent to bring human body and environment; Secondly, the poly butylene succinate of the molten state obtaining is purified without dissolving sedimentation, be directly used in and cause rac-Lactide ring-opening polymerization, and the poly butylene succinate of molten state is not containing any moisture, therefore preparation method of the present invention does not need through dewatering dry, simplify preparation technology, reduced production cost.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the poly butylene succinate 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 preparation in the embodiment of the present invention 1.
Embodiment
The preparation method who the invention provides a kind of polylactic-acid block copolymer, comprises the following steps: A) succinic acid and butyleneglycol are reacted under the effect of the first catalyzer, obtain the poly butylene succinate of molten state; B) poly butylene succinate of described molten state is reacted under the effect of the second catalyzer with rac-Lactide, obtain the polylactic-acid block copolymer shown in formula (I).
Formula (I), p=20 ~ 1600, are preferably 40 ~ 1400, and more preferably 60 ~ 1200, m=20 ~ 300, are preferably 40 ~ 250, and more preferably 80 ~ 200.
The present invention need be directly used in the poly butylene succinate of the molten state obtaining and cause rac-Lactide ring-opening polymerization, as intercooling solidifies, reheat molten state and can absorb moisture, must be dry through thoroughly dewatering, can cause that this step is consuming time and difficulty is large, poly butylene succinate remains molten state not containing any moisture, therefore do not need through except water treatment, simplified production technique.
Wherein, described the first catalyzer is one or more in tetrabutyl titanate, tin protochloride, isopropyl titanate, stannous octoate, zinc acetate and tosic acid, be preferably one or more in tetrabutyl titanate, tin protochloride, isopropyl titanate and stannous octoate, more preferably tetrabutyl titanate or stannous octoate, the quality of the first catalyzer is 0.01% ~ 1% of succinic acid quality, be preferably 0.05% ~ 1%, more preferably 0.05% ~ 0.8%, be preferably again 0.05% ~ 0.5%, most preferably be 0.05% ~ 0.2%.
Described the second catalyzer is aluminum isopropylate, divinyl zinc, tin protochloride or stannous octoate, be preferably aluminum isopropylate, tin protochloride or stannous octoate, stannous octoate more preferably, the quality of the second catalyzer is 0.01% ~ 1% of rac-Lactide quality, more preferably 0.08% ~ 0.8%, be preferably again 0.09% ~ 0.5%, most preferably be 0.09% ~ 0.2%.
In order to clearly demonstrate the present invention, below respectively the experimentation of steps A and step B is described in detail.
According to the present invention, described steps A is specially: under the condition of the first catalyzer and protection of inert gas, by succinic acid and butyleneglycol according to mol ratio 1:(1 ~ 2) ratio carry out mix and blend, be preferably 1:(1 ~ 1.5), make it to occur esterification, collect the water that reaction generates simultaneously, to no longer including liquid in reaction system, distillate, then being evacuated to pressure is that 10 ~ 300Pa carries out polycondensation, be preferably 30 ~ 250Pa, 50 ~ 200Pa more preferably, be preferably again 80 ~ 150Pa, when stirring velocity obvious when slack-off, stirring voltage is increased to definite value, be preferably 80 ~ 220V, 80 ~ 180V more preferably, and record agitator revolution, treat that stirring velocity is stable, this step finishes.Described inert protective gas is rare gas element well known to those skilled in the art, is preferably nitrogen or argon gas.
The temperature of reaction of esterification described in steps A is 130 ℃ ~ 230 ℃, be preferably 130 ℃ ~ 200 ℃, more preferably 130 ℃ ~ 180 ℃, reaction times is that 1 ~ 8h no longer includes liquid and distillates in reaction system, be preferably 3 ~ 5h, in this reaction, succinic acid reacts with butyleneglycol and generates succinic acid-butanediol ester.The temperature of reaction of described polycondensation is 210 ℃ ~ 270 ℃, is preferably 210 ℃ ~ 250 ℃, and the reaction times is 2 ~ 24h, and the revolution of agitator is stable, is preferably 4 ~ 20h, 8 ~ 16h more preferably, then be preferably 10 ~ 14h.
The present invention adopts one kettle way to be prepared polylactic-acid block copolymer, the poly butylene succinate of the molten state obtaining in steps A is without purifying through modes such as dissolution precipitations, be directly used in step B and rac-Lactide ring-opening polymerization, in reinforced process, poly butylene succinate must remain molten state.
According to the present invention; described step B is specially: rac-Lactide and the second catalyzer are added in poly butylene succinate; under the condition of protection of inert gas, react, reaction finishes the rear devolatilization processing of directly carrying out, and obtains the polylactic-acid block copolymer shown in formula (I).The mass ratio of described rac-Lactide and poly butylene succinate is (1 ~ 81): 9, be preferably (1 ~ 54): and 9, more preferably (10 ~ 45): 9.
Reaction in described step B is rac-Lactide ring-opening polymerization, and the temperature of reaction of described reaction is 100 ℃ ~ 180 ℃, is preferably 100 ℃ ~ 160 ℃, more preferably 100 ℃ ~ 140 ℃, the reaction times is 5 ~ 48h, is preferably 8 ~ 40h, 12 ~ 35h more preferably, then be preferably 16 ~ 30h.
Due to rac-Lactide ring-opening polymerization employing in the present invention is mass polymerization, and under the temperature condition of the present invention's reaction, poly butylene succinate and rac-Lactide are molten state, both itself can be used as solvent, therefore do not need to add in addition any organic solvent, reduced production cost, the harm of having avoided organic solvent volatilization to bring environment and human body.
After step B reaction finishes, directly carry out devolatilization processing, be preferably logical nitrogen devolatilization, remove unreacted monomer, extruding pelletization, obtains the poly(lactic acid)-poly butylene succinate segmented copolymer shown in formula (I), also without adopting modes such as dissolving sedimentation to purify.
The present invention is one pot reaction, reacts continuously, and intermediate product poly butylene succinate does not need through any processing, is directly used in next step rac-Lactide ring-opening polymerization.Steps A and step B can react continuously in same reactor, also can after steps A finishes, product be transferred to and in another one reactor, proceed next step reaction.
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
1.1 repeatedly vacuum nitrogen filling gas 2L is carried out cooling with the reactor of four-way gas port, be filled with nitrogen, add 59g succinic acid, 45g butyleneglycol and 0.05g tetrabutyl titanate, mix and blend is also warming up to rapidly 130 ℃, collect the water producing in reaction system simultaneously, extremely in reaction, no longer including liquid distillates, progressively be warming up to 210 ℃, vacuumize and react, obvious when slack-off until agitator speed, progressively strengthen and stir voltage to 120V, record agitator revolution, to stirring revolution, no longer reduce and reach definite value, obtain the poly butylene succinate of molten state.
1.2 by the poly butylene succinate of the molten state obtaining in 80g 1.1,320g rac-Lactide and 0.32g stannous octoate, at 120 ℃, react, after reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains polylactic-acid block copolymer, and weight average molecular mass is 100.0kg/mol relatively, relative molecular weight is distributed as 1.70, and relative molecular weight is distributed as symmetrical peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in 1.2, obtaining its fusing point is 170 ℃, and second-order transition temperature is 62.6 ℃, and heat decomposition temperature is 272 ℃.
Utilize nucleus magnetic resonance respectively the polylactic-acid block copolymer obtaining in the poly butylene succinate and 1.2 obtaining in 1.1 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 butylene succinate, Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of polylactic-acid block copolymer, a in figure, b, c is respectively the displacement of different hydro in polymkeric substance.
Embodiment 2
2.1 repeatedly vacuum nitrogen filling gas 2L is carried out cooling with the reactor of four-way gas port, be filled with nitrogen, add 59g succinic acid, 45g butyleneglycol and 0.05g tetrabutyl titanate, mix and blend is also warming up to rapidly 130 ℃, collect the water producing in reaction system simultaneously, extremely in reaction, no longer including liquid distillates, progressively be warming up to 210 ℃, vacuumize and react, obvious when slack-off until agitator speed, progressively strengthen and stir voltage to 120V, record agitator revolution, to stirring revolution, no longer reduce and reach definite value, obtain the poly butylene succinate of molten state.
2.2 by the poly butylene succinate of the molten state obtaining in 80g 2.1,240g rac-Lactide and 0.24g stannous octoate, at 120 ℃, react, after reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains polylactic-acid block copolymer, and weight average molecular mass is 90.0kg/mol relatively, relative molecular weight is distributed as 1.80, and relative molecular weight is distributed as symmetrical peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in 2.2, obtaining its fusing point is 170 ℃, and second-order transition temperature is 62.0 ℃, and heat decomposition temperature is 272 ℃.
Embodiment 3
3.1 repeatedly vacuum nitrogen filling gas 2L is carried out cooling with the reactor of four-way gas port, be filled with nitrogen, add 59g succinic acid, 45g butyleneglycol and 0.05g tetrabutyl titanate, mix and blend is also warming up to rapidly 130 ℃, collect the water producing in reaction system simultaneously, extremely in reaction, no longer including liquid distillates, progressively be warming up to 210 ℃, vacuumize and react, obvious when slack-off until agitator speed, progressively strengthen and stir voltage to 120V, record agitator revolution, to stirring revolution, no longer reduce and reach definite value, obtain the poly butylene succinate of molten state.
3.2 by the poly butylene succinate of the molten state obtaining in 80g 3.1,120g rac-Lactide and 0.12g stannous octoate, at 120 ℃, react, after reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains polylactic-acid block copolymer, and weight average molecular mass is 50.0kg/mol relatively, relative molecular weight is distributed as 1.80, and relative molecular weight is distributed as symmetrical peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in 3.2, obtaining its fusing point is 170 ℃, and second-order transition temperature is 61.1 ℃, and heat decomposition temperature is 271 ℃.
Embodiment 4
4.1 repeatedly vacuum nitrogen filling gas 2L is carried out cooling with the reactor of four-way gas port, be filled with nitrogen, add 59g succinic acid, 54g butyleneglycol and 0.05g tetrabutyl titanate, mix and blend is also warming up to rapidly 130 ℃, collect the water producing in reaction system simultaneously, extremely in reaction, no longer including liquid distillates, progressively be warming up to 210 ℃, vacuumize and react, obvious when slack-off until agitator speed, progressively strengthen and stir voltage to 120V, record agitator revolution, to stirring revolution, no longer reduce and reach definite value, obtain the poly butylene succinate of molten state.
4.2 by the poly butylene succinate of the molten state obtaining in 82g 4.1,328g rac-Lactide and 0.328g stannous octoate, at 120 ℃, react, after reaction 16h, logical nitrogen devolatilization, extruding pelletization, obtains polylactic-acid block copolymer, and weight average molecular mass is 120.0kg/mol relatively, relative molecular weight is distributed as 1.75, and relative molecular weight is distributed as symmetrical peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in 4.2, obtaining its fusing point is 170 ℃, and second-order transition temperature is 62.5 ℃, and heat decomposition temperature is 272 ℃.
Embodiment 5
5.1 repeatedly vacuum nitrogen filling gas 2L is carried out cooling with the reactor of four-way gas port, be filled with nitrogen, add 59g succinic acid, 54g butyleneglycol and 0.05g tetrabutyl titanate, mix and blend is also warming up to rapidly 130 ℃, collect the water producing in reaction system simultaneously, extremely in reaction, no longer including liquid distillates, progressively be warming up to 210 ℃, vacuumize and react, obvious when slack-off until agitator speed, progressively strengthen and stir voltage to 120V, record agitator revolution, to stirring revolution, no longer reduce and reach definite value, obtain the poly butylene succinate of molten state.
5.2 by the poly butylene succinate of the molten state obtaining in 82g 5.1,246g rac-Lactide and 0.246g stannous octoate, at 120 ℃, react, after reaction 16h, logical nitrogen devolatilization, extruding pelletization, obtains polylactic-acid block copolymer, and weight average molecular mass is 110.0kg/mol relatively, relative molecular weight is distributed as 1.81, and relative molecular weight is distributed as symmetrical peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in 5.2, obtaining its fusing point is 170 ℃, and second-order transition temperature is 62.3 ℃, and heat decomposition temperature is 272 ℃.
Embodiment 6
6.1 repeatedly vacuum nitrogen filling gas 2L is carried out cooling with the reactor of four-way gas port, be filled with nitrogen, add 59g succinic acid, 54g butyleneglycol and 0.05g tetrabutyl titanate, mix and blend is also warming up to rapidly 130 ℃, collect the water producing in reaction system simultaneously, extremely in reaction, no longer including liquid distillates, progressively be warming up to 210 ℃, vacuumize and react, obvious when slack-off until agitator speed, progressively strengthen and stir voltage to 120V, record agitator revolution, to stirring revolution, no longer reduce and reach definite value, obtain the poly butylene succinate of molten state.
6.2 by the poly butylene succinate of the molten state obtaining in 82g 6.1,123g rac-Lactide and 0.123g stannous octoate, at 120 ℃, react, after reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains polylactic-acid block copolymer, and weight average molecular mass is 90.0kg/mol relatively, relative molecular weight is distributed as 1.77, and relative molecular weight is distributed as symmetrical peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in 6.2, obtaining its fusing point is 170 ℃, and second-order transition temperature is 61.9 ℃, and heat decomposition temperature is 272 ℃.
Embodiment 7
7.1 repeatedly vacuum nitrogen filling gas 2L is carried out cooling with the reactor of four-way gas port, be filled with nitrogen, add 59g succinic acid, 54g butyleneglycol and 0.1g tetrabutyl titanate, mix and blend is also warming up to rapidly 130 ℃, collect the water producing in reaction system simultaneously, extremely in reaction, no longer including liquid distillates, progressively be warming up to 210 ℃, vacuumize and react, obvious when slack-off until agitator speed, progressively strengthen and stir voltage to 120V, record agitator revolution, to stirring revolution, no longer reduce and reach definite value, obtain the poly butylene succinate of molten state.
7.2 by the poly butylene succinate of the molten state obtaining in 83g 7.1,328g rac-Lactide and 0.328g stannous octoate, at 120 ℃, react, after reaction 13h, logical nitrogen devolatilization, extruding pelletization, obtains polylactic-acid block copolymer, and weight average molecular mass is 125.0kg/mol relatively, relative molecular weight is distributed as 1.78, and relative molecular weight is distributed as symmetrical peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in 7.2, obtaining its fusing point is 170 ℃, and second-order transition temperature is 62.4 ℃, and heat decomposition temperature is 272 ℃.
Embodiment 8
8.1 repeatedly vacuum nitrogen filling gas 2L is carried out cooling with the reactor of four-way gas port, be filled with nitrogen, add 59g succinic acid, 54g butyleneglycol and 0.1g tetrabutyl titanate, mix and blend is also warming up to rapidly 130 ℃, collect the water producing in reaction system simultaneously, extremely in reaction, no longer including liquid distillates, progressively be warming up to 210 ℃, vacuumize and react, obvious when slack-off until agitator speed, progressively strengthen and stir voltage to 120V, record agitator revolution, to stirring revolution, no longer reduce and reach definite value, obtain the poly butylene succinate of molten state.
8.2 by the poly butylene succinate of the molten state obtaining in 83g 8.1,246g rac-Lactide and 0.246g stannous octoate, at 120 ℃, react, after reaction 13h, logical nitrogen devolatilization, extruding pelletization, obtains polylactic-acid block copolymer, and weight average molecular mass is 110.0kg/mol relatively, relative molecular weight is distributed as 1.79, and relative molecular weight is distributed as symmetrical peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in 8.2, obtaining its fusing point is 170 ℃, and second-order transition temperature is 62.0 ℃, and heat decomposition temperature is 272 ℃.
Embodiment 9
9.1 repeatedly vacuum nitrogen filling gas 2L is carried out cooling with the reactor of four-way gas port, be filled with nitrogen, add 59g succinic acid, 45g butyleneglycol and 0.05g tetrabutyl titanate, mix and blend is also warming up to rapidly 150 ℃, collect the water producing in reaction system simultaneously, extremely in reaction, no longer including liquid distillates, progressively be warming up to 210 ℃, vacuumize and react, obvious when slack-off until agitator speed, progressively strengthen and stir voltage to 120V, record agitator revolution, to stirring revolution, no longer reduce and reach definite value, obtain the poly butylene succinate of molten state.
9.2 by the poly butylene succinate of the molten state obtaining in 83g 9.1,332g rac-Lactide and 0.332g stannous octoate, at 120 ℃, react, after reaction 13h, logical nitrogen devolatilization, extruding pelletization, obtains polylactic-acid block copolymer, and weight average molecular mass is 130.0kg/mol relatively, relative molecular weight is distributed as 1.70, and relative molecular weight is distributed as symmetrical peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in 9.2, obtaining its fusing point is 170 ℃, and second-order transition temperature is 62.6 ℃, and heat decomposition temperature is 272 ℃.
Embodiment 10
10.1 repeatedly vacuum nitrogen filling gas 2L is carried out cooling with the reactor of four-way gas port, be filled with nitrogen, add 59g succinic acid, 45g butyleneglycol and 0.05g tetrabutyl titanate, mix and blend is also warming up to rapidly 150 ℃, collect the water producing in reaction system simultaneously, extremely in reaction, no longer including liquid distillates, progressively be warming up to 210 ℃, vacuumize and react, obvious when slack-off until agitator speed, progressively strengthen and stir voltage to 120V, record agitator revolution, to stirring revolution, no longer reduce and reach definite value, obtain the poly butylene succinate of molten state.
10.2 by the poly butylene succinate of the molten state obtaining in 83g 10.1,249g rac-Lactide and 0.249g stannous octoate, at 120 ℃, react, after reaction 13h, logical nitrogen devolatilization, extruding pelletization, obtains polylactic-acid block copolymer, and weight average molecular mass is 100.0kg/mol relatively, relative molecular weight is distributed as 1.82, and relative molecular weight is distributed as symmetrical peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in 10.2, obtaining its fusing point is 170 ℃, and second-order transition temperature is 62.2 ℃, and heat decomposition temperature is 272 ℃.
Embodiment 11
11.1 repeatedly vacuum nitrogen filling gas 2L is carried out cooling with the reactor of four-way gas port, be filled with nitrogen, add 59g succinic acid, 45g butyleneglycol and 0.05g tetrabutyl titanate, mix and blend is also warming up to rapidly 150 ℃, collect the water producing in reaction system simultaneously, extremely in reaction, no longer including liquid distillates, progressively be warming up to 240 ℃, vacuumize and react, obvious when slack-off until agitator speed, progressively strengthen and stir voltage to 120V, record agitator revolution, to stirring revolution, no longer reduce and reach definite value, obtain the poly butylene succinate of molten state.
11.2 by the poly butylene succinate of the molten state obtaining in 84g 11.1,336g rac-Lactide and 0.336g stannous octoate, at 120 ℃, react, after reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains polylactic-acid block copolymer, and weight average molecular mass is 133.0kg/mol relatively, relative molecular weight is distributed as 1.81, and relative molecular weight is distributed as symmetrical peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in 11.2, obtaining its fusing point is 170 ℃, and second-order transition temperature is 62.6 ℃, and heat decomposition temperature is 272 ℃.
Embodiment 12
12.1 repeatedly vacuum nitrogen filling gas 2L is carried out cooling with the reactor of four-way gas port, be filled with nitrogen, add 59g succinic acid, 45g butyleneglycol and 0.05g tetrabutyl titanate, mix and blend is also warming up to rapidly 150 ℃, collect the water producing in reaction system simultaneously, extremely in reaction, no longer including liquid distillates, progressively be warming up to 240 ℃, vacuumize and react, obvious when slack-off until agitator speed, progressively strengthen and stir voltage to 120V, record agitator revolution, to stirring revolution, no longer reduce and reach definite value, obtain the poly butylene succinate of molten state.
12.2 by the poly butylene succinate of the molten state obtaining in 84g 12.1,252g rac-Lactide and 0.252g stannous octoate, at 120 ℃, react, after reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains polylactic-acid block copolymer, and weight average molecular mass is 113.0kg/mol relatively, relative molecular weight is distributed as 1.79, and relative molecular weight is distributed as symmetrical peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in 12.2, obtaining its fusing point is 170 ℃, and second-order transition temperature is 62.5 ℃, and heat decomposition temperature is 272 ℃.
Embodiment 13
13.1 repeatedly vacuum nitrogen filling gas 2L is carried out cooling with the reactor of four-way gas port, be filled with nitrogen, add 59g succinic acid, 54g butyleneglycol and 0.1g tetrabutyl titanate, mix and blend is also warming up to rapidly 150 ℃, collect the water producing in reaction system simultaneously, extremely in reaction, no longer including liquid distillates, progressively be warming up to 240 ℃, vacuumize and react, obvious when slack-off until agitator speed, progressively strengthen and stir voltage to 120V, record agitator revolution, to stirring revolution, no longer reduce and reach definite value, obtain the poly butylene succinate of molten state.
13.2 by the poly butylene succinate of the molten state obtaining in 85g 13.1,340g rac-Lactide and 0.34g stannous octoate, at 120 ℃, react, after reaction 13h, logical nitrogen devolatilization, extruding pelletization, obtains polylactic-acid block copolymer, and weight average molecular mass is 140.0kg/mol relatively, relative molecular weight is distributed as 1.83, and relative molecular weight is distributed as symmetrical peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in 13.2, obtaining its fusing point is 170 ℃, and second-order transition temperature is 62.7 ℃, and heat decomposition temperature is 272 ℃.
Embodiment 14
14.1 repeatedly vacuum nitrogen filling gas 2L is carried out cooling with the reactor of four-way gas port, be filled with nitrogen, add 59g succinic acid, 54g butyleneglycol and 0.05g tetrabutyl titanate, mix and blend is also warming up to rapidly 150 ℃, collect the water producing in reaction system simultaneously, extremely in reaction, no longer including liquid distillates, progressively be warming up to 240 ℃, vacuumize and react, obvious when slack-off until agitator speed, progressively strengthen and stir voltage to 120V, record agitator revolution, to stirring revolution, no longer reduce and reach definite value, obtain the poly butylene succinate of molten state.
14.2 by the poly butylene succinate of the molten state obtaining in 85g 14.1,170g rac-Lactide and 0.17g stannous octoate, at 120 ℃, react, after reaction 12h, logical nitrogen devolatilization, extruding pelletization, obtains polylactic-acid block copolymer, and weight average molecular mass is 100.0kg/mol relatively, relative molecular weight is distributed as 1.78, and relative molecular weight is distributed as symmetrical peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in 14.2, obtaining its fusing point is 170 ℃, and second-order transition temperature is 62.2 ℃, and heat decomposition temperature is 272 ℃.
Embodiment 15
15.1 repeatedly vacuum nitrogen filling gas 2L is carried out cooling with the reactor of four-way gas port, be filled with nitrogen, add 59g succinic acid, 54g butyleneglycol and 0.05g tetrabutyl titanate, mix and blend is also warming up to rapidly 180 ℃, collect the water producing in reaction system simultaneously, extremely in reaction, no longer including liquid distillates, progressively be warming up to 240 ℃, vacuumize and react, obvious when slack-off until agitator speed, progressively strengthen and stir voltage to 120V, record agitator revolution, to stirring revolution, no longer reduce and reach definite value, obtain the poly butylene succinate of molten state.
15.2 by the poly butylene succinate of the molten state obtaining in 83g 15.1,332g rac-Lactide and 0.332g stannous octoate, at 120 ℃, react, after reaction 13h, logical nitrogen devolatilization, extruding pelletization, obtains polylactic-acid block copolymer, and weight average molecular mass is 135.0kg/mol relatively, relative molecular weight is distributed as 1.86, and relative molecular weight is distributed as symmetrical peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in 15.2, obtaining its fusing point is 170 ℃, and second-order transition temperature is 62.6 ℃, and heat decomposition temperature is 272 ℃.
Embodiment 16
16.1 repeatedly vacuum nitrogen filling gas 2L is carried out cooling with the reactor of four-way gas port, be filled with nitrogen, add 59g succinic acid, 67.5g butyleneglycol and 0.05g tetrabutyl titanate, mix and blend is also warming up to rapidly 150 ℃, collect the water producing in reaction system simultaneously, extremely in reaction, no longer including liquid distillates, progressively be warming up to 240 ℃, vacuumize and react, obvious when slack-off until agitator speed, progressively strengthen and stir voltage to 120V, record agitator revolution, to stirring revolution, no longer reduce and reach definite value, obtain the poly butylene succinate of molten state.
16.2 by the poly butylene succinate of the molten state obtaining in 86g 16.1,344g rac-Lactide and 0.344g stannous octoate, at 120 ℃, react, after reaction 13h, logical nitrogen devolatilization, extruding pelletization, obtains polylactic-acid block copolymer, and weight average molecular mass is 134.0kg/mol relatively, relative molecular weight is distributed as 1.81, and relative molecular weight is distributed as symmetrical peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in 16.2, obtaining its fusing point is 170 ℃, and second-order transition temperature is 62.6 ℃, and heat decomposition temperature is 272 ℃.
Embodiment 17
17.1 repeatedly vacuum nitrogen filling gas 2L is carried out cooling with the reactor of four-way gas port, be filled with nitrogen, add 59g succinic acid, 67.5g butyleneglycol and 0.05g tetrabutyl titanate, mix and blend is also warming up to rapidly 150 ℃, collect the water producing in reaction system simultaneously, extremely in reaction, no longer including liquid distillates, progressively be warming up to 240 ℃, vacuumize and react, obvious when slack-off until agitator speed, progressively strengthen and stir voltage to 120V, record agitator revolution, to stirring revolution, no longer reduce and reach definite value, obtain the poly butylene succinate of molten state.
17.2 by the poly butylene succinate of the molten state obtaining in 86g 17.1,258g rac-Lactide and 0.252g stannous octoate, at 120 ℃, react, after reaction 16h, logical nitrogen devolatilization, extruding pelletization, obtains polylactic-acid block copolymer, and weight average molecular mass is 110.0kg/mol relatively, relative molecular weight is distributed as 1.78, and relative molecular weight is distributed as symmetrical peak.
Utilize differential scanning calorimeter (DSC) to analyze the polylactic-acid block copolymer obtaining in 17.2, obtaining its fusing point is 170 ℃, and second-order transition temperature is 62.5 ℃, and heat decomposition temperature is 272 ℃.
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 (4)
1. a preparation method for polylactic-acid block copolymer, is characterized in that, comprises the following steps:
A) under the condition of protection of inert gas, succinic acid and butyleneglycol are carried out to esterification under the effect of the first catalyzer, after vacuumizing, carry out polycondensation, obtain the poly butylene succinate of molten state; Described the first catalyzer is one or more in tetrabutyl titanate, tin protochloride, isopropyl titanate, stannous octoate, zinc acetate and tosic acid; The temperature of reaction of described esterification is 130 ℃～230 ℃, and the reaction times is 1～8h; The temperature of reaction of described polycondensation is 210 ℃～270 ℃, and the reaction times is 2～24h, and reaction pressure is 10～300Pa;
B) poly butylene succinate of described molten state is reacted under the effect of the second catalyzer with rac-Lactide, obtain polylactic-acid block copolymer, described the second catalyzer is aluminum isopropylate, divinyl zinc, tin protochloride or stannous octoate; The temperature of reaction of reacting in described step B is 100 ℃～180 ℃, and the reaction times is 5～48h.
2. preparation method according to claim 1, is characterized in that, the mass ratio of described the first catalyzer and succinic acid is (0.01～1): 100.
3. preparation method according to claim 1, is characterized in that, the mass ratio of described rac-Lactide and poly butylene succinate is (1～81): 9.
4. preparation method according to claim 1, is characterized in that, the mass ratio of described the second catalyzer and rac-Lactide is (0.01～1): 100.
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| CN103772677B (en) * | 2013-12-23 | 2015-12-02 | 中国科学院长春应用化学研究所 | A kind of polylactic-acid block copolymer and preparation method thereof |
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| CN103804660B (en) * | 2014-03-04 | 2016-02-03 | 中国科学院长春应用化学研究所 | A kind of unsaturated aliphatic-polylactic-acid block copolymer and preparation method thereof |
| CN103937184B (en) * | 2014-05-07 | 2016-03-30 | 江苏科技大学 | The poly (lactic acid) composition of a kind of high strength and high tenacity degradable and reactive extrursion preparation method thereof |
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| CN105418900B (en) * | 2016-01-12 | 2017-07-28 | 中国科学院长春应用化学研究所 | The preparation method of poly butylene succinate and polylactic-acid block copolymer |
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| CN112062939B (en) * | 2020-09-15 | 2022-11-01 | 常州大学 | High-resilience polylactic acid block copolymer and preparation method thereof |
| CN113999373A (en) * | 2021-12-03 | 2022-02-01 | 辽宁东盛塑业有限公司 | Polylactic acid-polyethylene glycol succinate copolymer and preparation method thereof |
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