CN102838734A - Polylactic acid block polymer and preparation method thereof - Google Patents
Polylactic acid block polymer and preparation method thereof Download PDFInfo
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- CN102838734A CN102838734A CN2012103616139A CN201210361613A CN102838734A CN 102838734 A CN102838734 A CN 102838734A CN 2012103616139 A CN2012103616139 A CN 2012103616139A CN 201210361613 A CN201210361613 A CN 201210361613A CN 102838734 A CN102838734 A CN 102838734A
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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 the conventional plastic goods generally need to go up century-old even the longer time could degrade fully, have caused serious " white pollution "; Simultaneously the conventional plastic raw material all derives from Nonrenewable resources such as oil, along with the exhausted conventional plastic industry of petrochemical industry resource also is on the hazard.Therefore the friendly biodegradable polymkeric substance of development environment substitutes the petroleum-based plastics product energetically, has become the current research hot of research and development.
Wherein, POLYACTIC ACID (PLA) is very important a kind of bio-degradable plastics; Be that the lactic acid that refines with the agricultural-food corn is monomer; Through the new bio degradable high polymer material of chemosynthesis, have nontoxic, nonirritant, good biocompatibility, intensity is high and characteristics such as biodegradable and absorption, in wrapping material, biological medicine and pharmaceutical industry, have a wide range of applications.And the degradation speed of POLYACTIC ACID is very fast, mixes with mikrobe and compound organic waste materials, can within some months, resolve into CO
2And H
2O.Therefore strengthen polylactic acid-based Products Development and application, can solve " white pollution " that perplex environment protection for a long time, and to realizing that Sustainable development has great importance.
But because long-chain branch is few in the polylactic acid molecule chain; Shortcomings such as making it have that melt strength is low, strain hardening is not enough, toughness is relatively poor, lack flexibility and elasticity, tear strength is low; In thermoforming, be directed against the polymkeric substance that this type of POLYACTIC ACID is hard and crisp, melt strength is low; Moulding process can only be carried out in narrow TR, so its application receives certain restriction.And; Owing to do not contain functional group in the molecular chain of POLYACTIC ACID with reactive behavior; Be difficult for introducing long-chain branch, therefore need to seek suitable PLA modified method, under the condition that does not influence performances such as PLA biological degradability, biocompatibility, intensity, improve its shortcoming.
Gathering (hexanodioic acid-terephthalic acid)-butyleneglycol copolyesters (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 has combined the degradability and the excellent mechanics and the thermal property of aromatic polyester of aliphatic polyester, compares with PLA, has biodegradation rate and good snappiness faster.Research shows, after PBAT and the PLA blend, the storage modulus of blend and viscosity improve with the increase of PBAT content gradually, and the elongation at break of blend and shock strength all are improved.But the consistency of PLA and PBAT is relatively poor, and the product performance that physical blending obtains are unstable.
At present, to the problem of physical blending, Yuan Hua etc. have proposed adding chainextender hexamethylene diisocyanate, utilize the chain extending reaction between PLA and the PBAT, in the 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 broad that obtains.
Summary of the invention
In view of this, the technical problem that the present invention will solve is to provide a kind of polylactic-acid block copolymer and preparation method thereof, and this method is nontoxic.
The invention provides a kind of polylactic-acid block copolymer, shown in (I):
Wherein, p=20 ~ 1400, n=5 ~ 200, m=5 ~ 200.
The invention provides a kind of process for polylactic acid block copolymer production, may further comprise the steps:
To gather (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters, rac-Lactide and 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, said rac-Lactide is (1:9) ~ (9:1) with the mass ratio that gathers (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters.
Preferably, the quality of said first catalyzer is 0.01% ~ 1% of a rac-Lactide quality.
Preferably, said first catalyzer is selected from one or more in aluminum isopropylate, divinyl zinc, tin protochloride and the stannous octoate.
Preferably, the temperature of reaction of said reaction is 80 ℃ ~ 180 ℃, and the reaction times is 3 ~ 50h.
Preferably, (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters prepares according to following steps said gathering:
With terephthaldehyde's acid source, hexanodioic acid, butyleneglycol and second catalyst mix; Carry out esterification and polycondensation successively; Gathered (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters, said terephthaldehyde's acid source is terephthalic acid and/or terephthalic acid ester derivative.
Preferably, said terephthaldehyde acid derivative is selected from one or more in DMT. Dimethyl p-benzenedicarboxylate, diethyl terephthalate, dioctyl terephthalate and the ethylene glycol terephthalate.
Preferably, the quality of said second catalyzer is 0.01% ~ 1% of terephthaldehyde's acid source and a hexanodioic acid total mass.
Preferably, said second catalyzer is selected from one or more in tetrabutyl titanate, tin protochloride, isopropyl titanate, stannous octoate, zinc acetate and the tosic acid.
The invention provides a kind of polylactic-acid block copolymer and preparation method thereof; This method will be gathered (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters, rac-Lactide and 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 the prior art vulcabond causes between PLA and the PBAT obtains the polymer phase ratio, and the present invention directly causes the polylactic-acid block copolymer that the rac-Lactide ring-opening polymerization obtains formula (I) structure with (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters that gathers of molten state.At first; The present invention directly causes the rac-Lactide ring-opening polymerization with (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters that gathers of molten state as reactant; Its polymerization method is mass polymerization; Do not add chainextender vulcabond and any organic solvent in the polymerization process, the harm of having avoided vulcabond and organic solvent that human body and environment are brought; Secondly, can obtain the polylactic-acid block copolymer of formula (I) structure after the raw materials mix reacting by heating of the present invention, the preparation method is simpler, and condition is gentle, has reduced preparation cost; Once more, 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 that obtains.
Experimental result shows that the polylactic-acid block copolymer MWD of the formula that the present invention prepares (I) structure is about 1.8, and fusing point is 172 ℃, and heat decomposition temperature is 275 ℃.
Description of drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram that gathers (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters of preparation in the embodiment of the 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 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 invention 1.
Embodiment
The invention provides a kind of polylactic-acid block copolymer, shown in (I):
Wherein, p==20 ~ 1400 are preferably 100 ~ 1200, and more preferably 200 ~ 1000, be preferably 400 ~ 800 again, n=5 ~ 200 are preferably 15 ~ 150, and more preferably 50 ~ 100, m=5 ~ 200 are preferably 20 ~ 160, and more preferably 40 ~ 120, be preferably 60 ~ 100 again.
The relative number average molecular weight of the polylactic-acid block copolymer of said formula (I) structure is 60 ~ 120kg/mol, is preferably 70 ~ 110kg/mol, more preferably 80 ~ 100kg/mol; 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 process for polylactic acid block copolymer production; May further comprise the steps: will gather (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters, rac-Lactide and 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 said formula (I) structure repeats no more at this with the above.
Rac-Lactide described in the present invention is (1:9) ~ (9:1) with the mass ratio that gathers (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters; Be preferably (1:1) ~ (6:1); More preferably (1.5:1) ~ (4:1) is preferably (1.5:1) ~ (3:1) again.Gather (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters and have snappiness preferably, cause rac-Lactide ring-opening polymerization formation segmented copolymer and can remedy the flexible and elastic shortcoming of POLYACTIC ACID shortage.
The quality of said first catalyzer is 0.01% ~ 1% of a rac-Lactide massfraction, is preferably 0.04% ~ 0.5%, more preferably 0.05% ~ 0.3%, be preferably 0.08% ~ 0.2% again.Said first catalyzer is the catalyzer of rac-Lactide ring-opening polymerization; Catalyzer for ring-opening polymerization well known to those skilled in the art; Said in the present invention first catalyzer is preferably selected from one or more in aluminum isopropylate, divinyl zinc, tin protochloride and the stannous octoate; More preferably tin protochloride or stannous octoate are preferably stannous octoate again.
According to the present invention, said reaction is the rac-Lactide ring-opening polymerization, and the temperature of reaction of said reaction is 80 ℃ ~ 180 ℃; Be preferably 90 ℃ ~ 160 ℃; More preferably 100 ℃ ~ 140 ℃, rac-Lactide is a molten state, and polymerization method is mass polymerization; Therefore need not to add vulcabond and any organic reagent, nontoxic.The reaction times of said reaction is 3 ~ 50h, is preferably 5 ~ 40h, and more preferably 7 ~ 30h is preferably 9 ~ 20h again.
After the rac-Lactide ring-opening polymerization finishes, preferably feed nitrogen and carry out devolatilization, remove unreacted monomer, extruding pelletization then obtains the polylactic-acid block copolymer of formula (I) structure.The method of said extruding pelletization does not have special limitation, is method well known to those skilled in the art.
According to the present invention; Said gathering, (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters preferably prepared according to following steps: with terephthaldehyde's acid source, hexanodioic acid, butyleneglycol and second catalyst mix; Carry out esterification and polycondensation successively, gathered (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters.Said terephthaldehyde's acid source is terephthalic acid and/or terephthalic acid ester derivative.
Said gathering (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters raw material terephthaldehyde acid source, hexanodioic acid and butyleneglycol between relationship between quality meet 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 relation between terephthaldehyde's acid source and the oxalic acid is that the ratio of its molar weight is (10:90) ~ (90:10).
Wherein, said terephthalic acid ester derivative is selected from one or more in DMT. Dimethyl p-benzenedicarboxylate, diethyl terephthalate, dioctyl terephthalate and the ethylene glycol terephthalate.
The quality of said second catalyzer is 0.01% ~ 1% of terephthaldehyde's acid source and a hexanodioic acid total mass, is preferably 0.04% ~ 0.6%, more preferably 0.05% ~ 0.4%, be preferably 0.06% ~ 0.2% again.Said second catalyzer is well known to those skilled in the art; Gather (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters synthetic in common catalyzer; Be preferably and be selected from tetrabutyl titanate, tin protochloride, isopropyl titanate, stannous octoate, zinc acetate and the tosic acid one or more; Be preferably and be selected from tetrabutyl titanate, tin protochloride, isopropyl titanate and the stannous octoate one or more, more preferably tetrabutyl titanate.
Esterification described in the present invention and polycondensation be well known to those skilled in the art gathering (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters synthetic in common reaction, do not have special limitation.
Esterification is preferably under the condition of normal pressure protection of inert gas and carries out among the present invention, and esterification reaction temperature is 140 ℃ ~ 230 ℃, is preferably 140 ℃ ~ 200 ℃, more preferably 140 ℃ ~ 180 ℃; The reaction times of esterification is preferably 1 ~ 8h for the water that produces in the reaction reaches theoretical aquifer yield, and more preferably 2 ~ 6h is preferably 4 ~ 5h again.Said inert protective gas is a rare gas element well known to those skilled in the art, is preferably nitrogen or argon gas.
Polycondensation is preferably carried out under vacuum low-pressure among the present invention, and the pressure of polycondensation is 10 ~ 250Pa, is preferably 50 ~ 200Pa, more preferably 80 ~ 150Pa; The temperature of reaction of said polycondensation is 210 ℃ ~ 280 ℃, is preferably 210 ℃ ~ 260 ℃, more preferably 210 ℃ ~ 240 ℃; The reaction times of said polycondensation is increased to definite value for stirring voltage, is preferably 80 ~ 220V, and 80 ~ 180V more preferably, and record whisking appliance revolution treats that stirring velocity is stable, and reaction finishes, and is preferably 2 ~ 48h, and more preferably 6 ~ 40h is preferably 10 ~ 30h again.
According to the present invention; Being preferably one kettle way reacts; It is synthetic to gather (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters and polylactic-acid block copolymer; Carry out successively, figure below is the response path of the polylactic-acid block copolymer of formula (I) structure, wherein gathers with phthalic acid, hexanodioic acid and butyleneglycol to be the synthetic used raw material of (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters.Gather (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters synthetic after; Need not to dissolve steps such as sedimentation and carry out purifying; Directly cool the temperature to 80 ℃ ~ 180 ℃, be preferably 90 ℃ ~ 160 ℃, more preferably 100 ℃ ~ 140 ℃; Add rac-Lactide and carry out ring-opening polymerization; This moment gathers (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters and rac-Lactide is molten state, and said ring-opening polymerization is mass polymerization, and (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters that gathers of molten state directly causes the rac-Lactide ring-opening polymerization as reactant; Need not to add chainextender vulcabond and any organic solvent in the polymerization process, the harm of having avoided vulcabond and organic solvent that human body and environment are brought; One kettle way reacts, and has omitted purification steps such as middle dissolving sedimentation, and condition is gentle, has reduced preparation cost.
Wherein, wherein, p=20 ~ 1400 are preferably 100 ~ 1200, and more preferably 200 ~ 1000, be preferably 400 ~ 800 again, n=5 ~ 200 are preferably 15 ~ 150, and more preferably 50 ~ 100, m=5 ~ 200 are preferably 20 ~ 160, and more preferably 40 ~ 120, be preferably 60 ~ 100 again.Y is the molar weight of butyleneglycol, adds according to the demand of esterification well known to those skilled in the art, does not have special limitation.
The result shows that the present invention adopts (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters that gathers of molten state directly to cause the rac-Lactide ring-opening polymerization as reactant, and the polylactic-acid block copolymer structure that obtains is clear and definite, and MWD is narrower.
In order to further specify the present invention, a kind of process for polylactic acid block copolymer production provided by the invention is described in detail below in conjunction with embodiment.
Used reagent is commercially available in following examples.
Embodiment 1
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 90g butyleneglycol and 0.1g tetrabutyl titanate added to have in the churned mechanically reaction kettle, be warming up to 140 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 210 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution, obtains; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.7g stannous octoate of crossing of 700g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number is 100.0kg/mol; Relative molecular weight is distributed as 1.75, and relative molecular weight is distributed as symmetric unimodal.
Utilize differential scanning calorimeter (DSC) that the polylactic-acid block copolymer that obtains among the embodiment 1 is analyzed, 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 the polylactic-acid block copolymer that gathers (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters and formula (I) structure that obtains among the embodiment 1 to be analyzed, obtain the hydrogen nuclear magnetic resonance spectrogram of two chemicals, as depicted in figs. 1 and 2; Fig. 1 is for gathering the hydrogen nuclear magnetic resonance spectrogram of (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters; Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the polylactic-acid block copolymer of formula (I) structure, a among the figure, b; C; D, e, f and g are respectively the displacement of different hydro in the polymkeric substance.
According to GB/T 1040-92 the polylactic-acid block copolymer of formula (I) structure that obtains among the embodiment 1 is carried out the tensile property test, obtain its stress-strain curve diagram, as shown in Figure 3.But the elongation at break of being invented the polylactic-acid block copolymer for preparing by Fig. 3 knowledge capital is compared with POLYACTIC 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 added to have in the churned mechanically reaction kettle, be warming up to 140 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 210 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.46g stannous octoate of crossing of 460g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number is 70.0kg/mol; Relative molecular weight is distributed as 1.78, and relative molecular weight is distributed as symmetric unimodal.
Utilize differential scanning calorimeter (DSC) that the polylactic-acid block copolymer that obtains among the embodiment 2 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 180 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 210 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.7g stannous octoate of crossing of 700g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 3 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 180 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 210 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.46g stannous octoate of crossing of 460g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 4 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 140 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 240 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.7g stannous octoate of crossing of 700g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 5 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 140 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 240 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.46g stannous octoate of crossing of 460g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 6 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 180 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 240 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.7g stannous octoate of crossing of 700g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 7 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 180 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 240 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.46g stannous octoate of crossing of 460g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 8 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 140 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 210 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.7g stannous octoate of crossing of 700g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number is 105.0kg/mol; Relative molecular weight is distributed as 1.73, and relative molecular weight is distributed as symmetric unimodal.
Utilize differential scanning calorimeter (DSC) that the polylactic-acid block copolymer that obtains among the embodiment 9 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 140 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 210 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.46g stannous octoate of crossing of 400g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number is 72.0kg/mol; Relative molecular weight is distributed as 1.78, and relative molecular weight is distributed as symmetric unimodal.
Utilize differential scanning calorimeter (DSC) that the polylactic-acid block copolymer that obtains among the embodiment 10 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 180 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 210 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.66g stannous octoate of crossing of 700g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 11 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 180 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 210 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.46g stannous octoate of crossing of 460g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 12 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 140 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 240 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.7g stannous octoate of crossing of 700g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 13 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 140 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 240 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.45g stannous octoate of crossing of 460g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 14 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 180 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 240 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.7g stannous octoate of crossing of 700g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 15 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 180 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 240 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.46g stannous octoate of crossing of 460g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 16 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 140 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 210 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.7g stannous octoate of crossing of 700g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number is 105.0kg/mol; Relative molecular weight is distributed as 1.79, and relative molecular weight is distributed as symmetric unimodal.
Utilize differential scanning calorimeter (DSC) that the polylactic-acid block copolymer that obtains among the embodiment 17 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 140 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 210 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.46g stannous octoate of crossing of 460g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number is 71.0kg/mol; Relative molecular weight is distributed as 1.83, and relative molecular weight is distributed as symmetric unimodal.
Utilize differential scanning calorimeter (DSC) that the polylactic-acid block copolymer that obtains among the embodiment 18 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 180 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 210 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.7g stannous octoate of crossing of 700g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 19 is analyzed, obtaining its fusing point is 172 ℃, and second-order transition temperature is 61.7 ℃, and heat decomposition temperature is 275 ℃.
Under the condition of nitrogen protection, 83g terephthalic acid, 73g hexanodioic acid, 135g butyleneglycol and 0.1g tetrabutyl titanate added to have in the churned mechanically reaction kettle, be warming up to 180 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 210 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.46g stannous octoate of crossing of 460g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 20 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 140 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 240 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.7g stannous octoate of crossing of 700g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 21 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 140 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 240 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.46g stannous octoate of crossing of 460g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 22 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 180 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 240 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.7g stannous octoate of crossing of 700g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 23 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 180 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 240 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.46g stannous octoate of crossing of 460g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 24 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 140 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 210 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.7g stannous octoate of crossing of 700g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number is 102.0kg/mol; Relative molecular weight is distributed as 1.75, and relative molecular weight is distributed as symmetric unimodal.
Utilize differential scanning calorimeter (DSC) that the polylactic-acid block copolymer that obtains among the embodiment 25 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 140 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 210 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.46g stannous octoate of crossing of 460g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number is 73.0kg/mol; Relative molecular weight is distributed as 1.78, and relative molecular weight is distributed as symmetric unimodal.
Utilize differential scanning calorimeter (DSC) that the polylactic-acid block copolymer that obtains among the embodiment 26 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 180 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 210 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.66g stannous octoate of crossing of 700g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 27 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 180 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 210 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.46g stannous octoate of crossing of 460g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 28 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 140 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 240 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.7g stannous octoate of crossing of 700g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 29 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 140 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 240 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.45g stannous octoate of crossing of 460g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 30 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 180 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 240 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.7g stannous octoate of crossing of 700g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 31 is analyzed, 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 added to have in the churned mechanically reaction kettle, be warming up to 180 ℃ under the normal pressure, carry out esterification, distillate moisture content, to reaching theoretical aquifer yield; Be warming up to 240 ℃ then, progressively being decompressed to high vacuum state pressure is 100Pa, carries out polycondensation, stirs voltage and establishes to 120V, and record whisking appliance revolution no longer reduces and reaches definite value to stirring revolution; Reduce temperature to 120 ℃, add dry rac-Lactide and the 0.46g stannous octoate of crossing of 460g, react 12h; Logical nitrogen devolatilization; Extruding pelletization obtains the polylactic-acid block copolymer of formula (I) structure, and the equal molecular mass of relative number 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) that the polylactic-acid block copolymer that obtains among the embodiment 32 is analyzed, obtaining its fusing point is 172 ℃, and second-order transition temperature is 62.1 ℃, and heat decomposition temperature is 275 ℃.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (10)
1. polylactic-acid block copolymer, shown in (I):
Wherein, p=20 ~ 1400, n=5 ~ 200, m=5 ~ 200.
2. a process for polylactic acid block copolymer production is characterized in that, may further comprise the steps:
To gather (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters, rac-Lactide and 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.
3. preparation method according to claim 2 is characterized in that, said rac-Lactide is (1:9) ~ (9:1) with the mass ratio that gathers (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters.
4. preparation method according to claim 2 is characterized in that, the quality of said first catalyzer is 0.01% ~ 1% of a rac-Lactide quality.
5. preparation method according to claim 2 is characterized in that, said first catalyzer is selected from one or more in aluminum isopropylate, divinyl zinc, tin protochloride and the stannous octoate.
6. preparation method according to claim 2 is characterized in that, the temperature of reaction of said reaction is 80 ℃ ~ 180 ℃, and the reaction times is 3 ~ 50h.
7. preparation method according to claim 2 is characterized in that, said gathering (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters prepare according to following steps:
With terephthaldehyde's acid source, hexanodioic acid, butyleneglycol and second catalyst mix; Carry out esterification and polycondensation successively; Gathered (hexanodioic acid-terephthalic acid) butyleneglycol copolyesters, said terephthaldehyde's acid source is terephthalic acid and/or terephthalic acid ester derivative.
8. preparation method according to claim 7 is characterized in that, said terephthaldehyde acid derivative is selected from one or more in DMT. Dimethyl p-benzenedicarboxylate, diethyl terephthalate, dioctyl terephthalate and the ethylene glycol terephthalate.
9. preparation method according to claim 7 is characterized in that, the quality of said second catalyzer is 0.01% ~ 1% of terephthaldehyde's acid source and a hexanodioic acid total mass.
10. preparation method according to claim 7 is characterized in that, said second catalyzer is selected from one or more in tetrabutyl titanate, tin protochloride, isopropyl titanate, stannous octoate, zinc acetate and the tosic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210361613.9A CN102838734B (en) | 2012-09-25 | 2012-09-25 | Polylactic acid block polymer and preparation method thereof |
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| CN103937184A (en) * | 2014-05-07 | 2014-07-23 | 江苏科技大学 | High-strength and high-toughness full-degradation polylactic acid composition and reaction extrusion preparation method thereof |
| 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 |
| CN105367770A (en) * | 2014-08-29 | 2016-03-02 | 中国科学院长春应用化学研究所 | Aliphatic-aromatic-polylactic acid block copolymer |
| CN105440605A (en) * | 2014-08-29 | 2016-03-30 | 中国科学院长春应用化学研究所 | Polylactic acid resin |
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| US10875958B2 (en) | 2017-07-11 | 2020-12-29 | Henan Green polymer co., Ltd | Method for synthesizing polybutylene adipate terephthalate-polylactic acid (PBAT-PLA) copolyester |
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