CN106700040A - Method for preparing polylactic acid through twin screw reactive extrusion method and ring open polymerization method - Google Patents
Method for preparing polylactic acid through twin screw reactive extrusion method and ring open polymerization method Download PDFInfo
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- CN106700040A CN106700040A CN201510516697.2A CN201510516697A CN106700040A CN 106700040 A CN106700040 A CN 106700040A CN 201510516697 A CN201510516697 A CN 201510516697A CN 106700040 A CN106700040 A CN 106700040A
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Abstract
The invention relates to a method for preparing polylactic acid with a twin screw reactive extrusion method and a ring open polymerization method. The raw materials comprise the following components in parts by weight: 120 parts of L-lactide, 8-10 parts of antioxidants and 0.3-0.8 part of a catalyst. According to the method for preparing polylactic acid through the twin screw reactive extrusion method and the ring open polymerization method provided by the invention, ring open polymerization of L-lactide is implemented to prepare the polylactic acid by taking a twin-screw extruder as a reactor, the optical purity, number-average molecular weight and heat-resistant number-average molecular weight of the polylactic acid are improved, and polylactic acid products of high molecular weight are obtained, so that the polylactic acid can be popularized and produced in batches, and the synthetic process is stable and reliable.
Description
Technical field
It is that a kind of ring-opening polymerisation with double screw extruder as reactor to implement L- lactides prepares PLA the present invention relates to pass through the method that twin-screw reactive extrursion method ring-opening polymerisation method prepares PLA, and in particular to macromolecular compound field.Its product is significantly increased in heat resistance, optical purity and number-average molecular weight.
Background technology
PLA (PLA), it is a kind of thermoplastic aliphatic's polyester of the degradable macromolecule material in polyester resin Material synthesis gone out produced in renewable resource, the features such as with nontoxic, nonirritant and good biocompatibility, biodegradability, machinability, in addition to the mankind are advantageously reduced to the dependence of petroleum resources；Carbon dioxide and water are can be biodegradable under field conditions (factors), it is highly beneficial to environmental protection.
The synthetic method of PLA (PLA) has two kinds of lactide ring-opening polymerisation method and acid through direct polycondensation by lactic method.Autoclave or tower reactor are used mostly in current industrialized production, the PLA of number-average molecular weight high is prepared by the ring-opening polymerisation of lactide, but often in 22 more than h, the Cost Problems brought under low production efficiency still limit poly-lactic acid products and move towards market on a large scale polymerization time.The shortcoming of acid through direct polycondensation by lactic method is that water is difficult to be discharged from reaction system as accessory substance, and hinder reaction is carried out to the direction of generation polymerizate, therefore is more difficult to get the polymerizate of number-average molecular weight high.
PLA (PLA) has excellent degradability and bio-compatibility, while possessing tensile strength higher, modulus of compressibility and good heat resistance, moreover it is possible to the advantages of being processed with various ways.But PLA (PLA) matter is hard and poor toughness, lack flexible and elasticity, easily flexural deformation, more because heat resisting temperature is too low (56 DEG C of softening point), this strongly limits it development and use scope, so needing to be modified PLA.The major technique for improving PLA heat resistance is the crystal property for improving PLA, improves the crystallinity of PLA.In addition, also have PLA and high glass transition temperature (Tg) macromolecular material are blended, introducing crosslinked structure, the method such as fiber reinforcement and nanometer composite technology.
In recent years, PLA is prepared using twin-screw reactive extrursion method by lactide ring-opening polymerisation gradually to be favored by researcher, the method has that production equipment and process flow is simple, reaction rate is fast, production efficiency is high, gained PLA product mechanical performance and the features such as good processability.
The technical problems to be solved by the invention are the defects for overcoming above-mentioned prior art to exist, one kind is provided with L- lactides as raw material, double screw extruder is reactor, to significantly improve the heat resistance of PLA, optical purity and number-average molecular weight, inquire into influence of the factor such as catalyst type and its content, polymerization time, polymerization temperature to polymerizate property.PLA is set to can manufacture and be promoted popularization.
The content of the invention
There is the defect of poor heat resistance for current PLA (PLA) material, the present invention proposes the method for preparing PLA by twin-screw reactive extrursion method ring-opening polymerisation method.To achieve the above object, the technical problem to be solved in the present invention is the defect for overcoming above-mentioned prior art to exist, one kind is provided with L- lactides as raw material, double screw extruder is reactor, to significantly improve the heat resistance of PLA, optical purity and number-average molecular weight, inquire into influence of the factor such as catalyst type and its content, polymerization time, polymerization temperature to polymerizate property.PLA (PLA) is set to can manufacture and be promoted popularization.
The method that the present invention prepares PLA by twin-screw reactive extrursion method ring-opening polymerisation method, it is characterised in that its each component is calculated as by weight：
120 parts of L- lactides
Antioxidant 8-10 parts
Catalyst 0.3-0.8 parts
Heretofore described polylactic acid raw material is L lactides.
One kind of heretofore described antioxidant 1010, irgasfos 168, antioxidant 626, antioxidant 1098 and TPH-24；
Heretofore described catalyst is Sn (Oct)2 /P( C6H5) 3、Sn( Oct) 2 /CH3 ( CH2) 11OH、Sn( Oct) 2, Ti ［ OCH (CH3) 2 4In one or more catalyst system and catalyzings；
Heretofore described processing technology is that the ring-opening polymerisation with double screw extruder as reactor to implement L- lactides prepares PLA.
The method that PLA is prepared by twin-screw reactive extrursion method ring-opening polymerisation method of the present invention, it is characterised in that specific preparation process is as follows：
（1）With toluene solvant by Sn (Oct)2And CH3 ( CH2) 11OH is according to mol ratio 1: 3
The solution that total concentration is 0.17mol/L is made into, and by Ti ［ OCH (CH3) 2 4Also it is made into 0.17 with toluene
, then be added in L- lactides for a certain amount of above-mentioned certain solution, appropriate antioxidant and be well mixed by the solution of mol/L, after the toluene in 4 h removing systems is evaporated in vacuo at 72 DEG C, is cooled to room temperature, vacuumizes encapsulation, stand-by.
（2）The ring-opening polymerisation of L- lactides
The ring-opening polymerisation of L- lactides is carried out in hing surface in the same direction.During polymerization, the above-mentioned L- lactides of catalyst that have been mixed with the uniform velocity are added to extrusion machine inlet under the protection of logical nitrogen, while being vacuumized in exhaust ports.During polymerization, screw speed is controlled in 110-150 r/min, and monomer by the polymerisation of certain hour in double screw extruder, by measuring pump extruded, and solid-state is cooled in atmosphere by polymerizate.
Extruder temperature is set as successively：160-170 DEG C, 165-175 DEG C, 175-185 DEG C, 180-190 DEG C, 175-1890 DEG C, 215-225 DEG C of die head temperature.
Specific embodiment
Below by way of specific embodiment, the present invention is described in further detail, but this should not be interpreted as into the scope of the present invention and be only limitted to following example.In the case where above method thought of the present invention is not departed from, according to various replacements or change that ordinary skill knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）With toluene solvant by Sn (Oct)2And CH3 ( CH2) 11OH is according to mol ratio 1: 2
The solution that total concentration is 0.17mol/L is made into, and by Ti ［ OCH (CH3) 2 4Also it is made into 0.17 with toluene
, then be added in L- lactides for a certain amount of above-mentioned certain solution, 6 parts of antioxidant TPH-24 and be well mixed by the solution of mol/L, after the toluene in 4 h removing systems is evaporated in vacuo at 72 DEG C, is cooled to room temperature, vacuumizes encapsulation, stand-by.
（2）The ring-opening polymerisation of L- lactides
The ring-opening polymerisation of L- lactides is carried out in screw slenderness ratio is for 49: 1 hing surface in the same direction, and the single screw diameter of double screw extruder is 22.5 mm, and two pitch distances are 18mm.During experiment, the above-mentioned L- lactides of catalyst that have been mixed with the uniform velocity are added to extrusion machine inlet under the protection of logical nitrogen, while being vacuumized in exhaust ports.During polymerization, screw speed is controlled 130
R/min, monomer by the polymerisation of certain hour in double screw extruder, by measuring pump extruded, and solid-state is cooled in atmosphere by polymerizate.
Extruder temperature is set as successively：160-170 DEG C, 165-175 DEG C, 175-185 DEG C, 180-190 DEG C, 175-1890 DEG C, 215-225 DEG C of die head temperature.
The poly-lactic acid products optical purity 92% for being obtained, number-average molecular weight 2.7 × 104, 65 DEG C of glass transition temperature, 170 DEG C of fusing point.
Embodiment 2
（1）With toluene solvant by Sn (Oct)2 /P( C6H5) 3According to mol ratio 1:
3 are made into the solution that total concentration is 0.17 mol/L, and by Ti ［ OCH (CH3) 2 4Also it is made into 0.17 with toluene
, then be added in L- lactides for a certain amount of above-mentioned certain solution, 3 parts of antioxidant 1010 and be well mixed, 72 by the solution of mol/L
After the toluene in 3 h removing systems is evaporated in vacuo at DEG C, room temperature is cooled to, vacuumizes encapsulation, it is stand-by.
（2）The ring-opening polymerisation of L- lactides
The ring-opening polymerisation of L- lactides is carried out in screw slenderness ratio is for 49: 1 hing surface in the same direction, and the single screw diameter of double screw extruder is 22.5 mm, and two pitch distances are 18mm.During experiment, the above-mentioned L- lactides of catalyst that have been mixed with the uniform velocity are added to extrusion machine inlet under the protection of logical nitrogen, while being vacuumized in exhaust ports.During polymerization, screw speed is controlled 130
R/min, monomer by the polymerisation of certain hour in double screw extruder, by measuring pump extruded, and solid-state is cooled in atmosphere by polymerizate.
Extruder temperature is set as successively：160-170 DEG C, 165-175 DEG C, 175-185 DEG C, 180-190 DEG C, 175-1890 DEG C, 215-225 DEG C of die head temperature.
The poly-lactic acid products optical purity 94% for being obtained, number-average molecular weight 3.2 × 104, 65 DEG C of glass transition temperature, 175 DEG C of fusing point.
Embodiment 3
（1）With toluene solvant by Sn (Oct)2And CH3 ( CH2) 11OH is according to mol ratio 1: 2
The solution that total concentration is 0.17mol/L is made into, and by Ti ［ OCH (CH3) 2 4Also it is made into 0.17 with toluene
, then be added in L- lactides for a certain amount of above-mentioned certain solution, 6 parts of antioxidant TPH-24 and be well mixed, 72 by the solution of mol/L
After the toluene in 4 h removing systems is evaporated in vacuo at DEG C, room temperature is cooled to, vacuumizes encapsulation, it is stand-by.
（2）The ring-opening polymerisation of L- lactides
The ring-opening polymerisation of L- lactides is carried out in screw slenderness ratio is for 49: 1 hing surface in the same direction, and the single screw diameter of double screw extruder is 21.5 mm, and two pitch distances are 18mm.During experiment, the above-mentioned L- lactides of catalyst that have been mixed with the uniform velocity are added to extrusion machine inlet under the protection of logical nitrogen, while being vacuumized in exhaust ports.During polymerization, screw speed is controlled 140
R/min, monomer by the polymerisation of certain hour in double screw extruder, by measuring pump extruded, and solid-state is cooled in atmosphere by polymerizate.
Extruder temperature is set as successively：160-170 DEG C, 165-175 DEG C, 175-185 DEG C, 180-190 DEG C, 175-1890 DEG C, 215-225 DEG C of die head temperature.
The poly-lactic acid products optical purity 99% for being obtained, number-average molecular weight 3.3 × 104, 76 DEG C of glass transition temperature, 182 DEG C of fusing point.
Claims (6)
1. the method for preparing PLA by twin-screw reactive extrursion method ring-opening polymerisation method, it is characterised in that the heat resistance of the PLA for being obtained, optical purity and number-average molecular weight are significantly improved, its material material weight portion composition is as follows：
120 parts of L- lactides
Antioxidant 8-10
Part
3-0.8 parts of catalyst 0..
2. the method that PLA is prepared by twin-screw reactive extrursion method ring-opening polymerisation method according to claim 1, it is characterised in that described polylactic acid raw material is L lactides.
3. the method that PLA is prepared by twin-screw reactive extrursion method ring-opening polymerisation method according to claim 1, it is characterised in that described antioxidant is antioxidant 1010, irgasfos 168, antioxidant 626, one kind of antioxidant 1098 and TPH-24.
4. the method that PLA is prepared by twin-screw reactive extrursion method ring-opening polymerisation method according to claim 1, it is characterised in that described catalyst is Sn (Oct)2 /P( C6H5) 3、Sn( Oct) 2 /CH3 ( CH2) 11OH、Sn( Oct) 2, Ti ［ OCH (CH3) 2 4In one or more catalyst system and catalyzings.
5. the method that PLA is prepared by twin-screw reactive extrursion method ring-opening polymerisation method according to claim 1, it is characterised in that described processing technology is that the ring-opening polymerisation using double screw extruder as reactor to implement L- lactides prepares PLA.
6. the method for PLA being prepared by twin-screw reactive extrursion method ring-opening polymerisation method according to claim 1, it is characterised in that specific preparation process is as follows：
（1）With toluene solvant by CH3 ( CH2) 11OH and CH3 ( CH2) 11OH is made into the solution that total concentration is 0.17 mol/L according to mol ratio 1: 3, and by Ti ［ OCH (CH3) 2 4Also the solution of 0.17 mol/L is made into toluene, then a certain amount of above-mentioned certain solution, appropriate antioxidant are added in L- lactides and are well mixed, after the toluene in 4 h removing systems is evaporated in vacuo at 72 DEG C, be cooled to room temperature, encapsulation is vacuumized, it is stand-by；
（2）The ring-opening polymerisation of L- lactides
The ring-opening polymerisation of L- lactides is carried out in hing surface in the same direction, and the above-mentioned L- lactides of catalyst that have been mixed with the uniform velocity are added to extrusion machine inlet under the protection of logical nitrogen, while being vacuumized in exhaust ports；During polymerization, screw speed is controlled in 110-150 r/min, and monomer by the polymerisation of certain hour in double screw extruder, by measuring pump extruded, and solid-state is cooled in atmosphere, and extruder temperature is set as successively by polymerizate：160-170 DEG C, 165-175 DEG C, 175-185 DEG C, 180-190 DEG C, 175-180 DEG C, 215-225 DEG C of die head temperature.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106893085A (en) * | 2015-12-18 | 2017-06-27 | 四川鑫达企业集团有限公司 | A kind of high-performance poly-lactic acid material and preparation method thereof |
| CN109280156A (en) * | 2018-09-13 | 2019-01-29 | 沈阳中博环保科技研发有限公司 | A method of poly-lactic acid in high molecular weight is prepared by double screw extruder |
| US11421350B2 (en) * | 2017-05-30 | 2022-08-23 | Teijin Frontier Co., Ltd. | Antibacterial electric charge generation yarn, method for manufacturing antibacterial electric charge generation yarn, and antibacterial cloth |
-
2015
- 2015-08-21 CN CN201510516697.2A patent/CN106700040A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106893085A (en) * | 2015-12-18 | 2017-06-27 | 四川鑫达企业集团有限公司 | A kind of high-performance poly-lactic acid material and preparation method thereof |
| US11421350B2 (en) * | 2017-05-30 | 2022-08-23 | Teijin Frontier Co., Ltd. | Antibacterial electric charge generation yarn, method for manufacturing antibacterial electric charge generation yarn, and antibacterial cloth |
| CN109280156A (en) * | 2018-09-13 | 2019-01-29 | 沈阳中博环保科技研发有限公司 | A method of poly-lactic acid in high molecular weight is prepared by double screw extruder |
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