CN109280156A - A method of poly-lactic acid in high molecular weight is prepared by double screw extruder - Google Patents
A method of poly-lactic acid in high molecular weight is prepared by double screw extruder Download PDFInfo
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- CN109280156A CN109280156A CN201811068025.XA CN201811068025A CN109280156A CN 109280156 A CN109280156 A CN 109280156A CN 201811068025 A CN201811068025 A CN 201811068025A CN 109280156 A CN109280156 A CN 109280156A
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- lactic acid
- molecular weight
- high molecular
- lactide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a kind of methods for preparing poly-lactic acid in high molecular weight by double screw extruder, prepare polylactic acid as reaction vessel using double screw extruder；Its feed components and parts by weight are as follows: 100 parts of lactide；0.2-0.4 parts of antioxidant；0.1-0.3 parts of catalyst；0.1-0.3 parts of lubricant.The problems such as present invention improves over traditional polylactic acid synthetic methods, realize that lactide ring-opening polymerisation prepares polylactic acid in double screw extruder, and it is low that this method solve molecular weight, are unable to continuous production；Production equipment and process process is simple, and reaction speed is fast, high production efficiency, and synthesis technology is more stable and reliable.
Description
Technical field
The present invention relates to a kind of methods for preparing poly-lactic acid in high molecular weight by double screw extruder, belong to high molecular material system
Make field.
Background technique
Polylactic acid (PLA) is a kind of thermoplastic polymer of novel environment friendly, its advantage is that having good biocompatibility
And biological degradability.Because it may participate in human metabolism etc. a little with nontoxic, catabolite, managed by U.S.'s food and medicine
Office's approval can be widely used for the fixed material of spansule, operation suture thread, orthopaedics and make as commodity polymer material etc.
With.
The synthetic method of polylactic acid (PLA) mainly has acid through direct polycondensation by lactic method and lactide ring-opening polymerisation method.It uses at present
More is lactide ring-opening polymerisation method, such as patent document WO90/01521 is described and produced poly- cream by lactide ring-opening polymerisation
The process of acid.Although the higher polylactic acid product of molecular weight can be obtained, the reaction time often will be at 24 hours or more, especially
It is that repeatedly in recrystallization, the low bring cost problem of production efficiency significantly limits lactide refined middle needs for purification
Poly-lactic acid products large-scale production；The major defect of acid through direct polycondensation by lactic method is water as by-product and is difficult to exclude from system,
It hinders reaction to carry out to the direction for generating polymer, it is more difficult to must fall the polymerizate of high molecular weight.
Polylactic acid is prepared by lactide open loop using twin-screw extrusion reaction method, not only production equipment is simple, Er Qiewu
It need to carry out repeatedly purifying and recrystallizing, greatly simplify the technological process of production, improve production efficiency, while also avoiding organic solvent
Use, the green safe environmental protection of production process.
The present invention adopts the following technical scheme:
The present invention prepares polylactic acid as reaction vessel using double screw extruder；Its feed components and parts by weight are as follows: third
It hands over
100 parts of ester；0.2-0.4 parts of antioxidant；0.1-0.3 parts of catalyst；0.1-0.3 parts of lubricant；The lactide is certainly
L- lactide processed；The antioxidant be antioxidant 1010, irgasfos 168, one of antioxidant 626 and antioxidant 1098 or
It is several；The catalyst is stannous octoate, in zinc oxide, one kind of stannous chloride；The lubricant is stearic acid, sweet
Oil, paraffin, epoxidized soybean oil, one or more of stearmide；
It is to prepare poly-lactic acid material using double screw extruder as reactor that the present invention, which processes reaction process,；
Steps are as follows for specific experiment of the present invention:
L- lactide, catalyst and antioxidant are uniformly mixed and are added to extrusion machine inlet, and logical nitrogen protection, is vented simultaneously
Mouth vacuumizes；When lactide ring-opening polymerisation.Screw speed is controlled in 100-120r/min, and polymer is squeezed out through metering pump,
Extrusion temperature is successively are as follows: and 150-160 DEG C, 165-175 DEG C, 175-185 DEG C, 185-190 DEG C, 180-185 DEG C, die head temperature 210-
220℃。
Beneficial effects of the present invention: the double screw extruder as reaction vessel has multiple exhaust outlets, reacts the pair of generation
Product water
It can be excluded immediately by exhaust outlet；And multiple unit segmentally heatings are used, temperature of each section passes through cooling cycle water energy
Enough independent progress, are precisely controlled reaction temperature；Product is purified without solvent, environmentally protective.
Specific embodiment
Embodiment 1
Each synthesizing polylactic acid material is pressed into component premix uniformly, feed components and parts by weight are as follows: lactide 100
Part, 0.2 part of antioxidant, 0.1 part of catalyst, 0.1 part of lubricant；
Pre- mixed material is at the uniform velocity added to extrusion machine inlet under logical nitrogen protection, while being vacuumized in exhaust ports,
Screw speed is controlled in 120r/min, and material is in double screw extruder after 15 hours polymerization reactions, and product is through metering pump
It squeezes out, is cooled to solid-state in air.Extrusion temperature is successively are as follows: and 150-160 DEG C, 165-175 DEG C, 175-185 DEG C, 185-190
DEG C, 180-185 DEG C, 210-220 DEG C of die head temperature.
Resulting poly-lactic acid products number-average molecular weight is 4.7 × 105。
Embodiment 2
Each synthesizing polylactic acid material is pressed into component premix uniformly, feed components and parts by weight are as follows: lactide 100
Part,
0.3 part of antioxidant, 0.2 part of catalyst, 0.2 part of lubricant；
Pre- mixed material is at the uniform velocity added to extrusion machine inlet under logical nitrogen protection, while being vacuumized in exhaust ports,
Screw speed is controlled in 120r/min, and material is in double screw extruder after 15 hours polymerization reactions, and product is through metering pump
It squeezes out, is cooled to solid-state in air.Extrusion temperature is successively are as follows: and 150-160 DEG C, 165-175 DEG C, 175-185 DEG C, 185-190
DEG C, 180-185 DEG C, 210-220 DEG C of die head temperature.
Resulting poly-lactic acid products number-average molecular weight is 6.8 × 105
Embodiment 3
Each synthesizing polylactic acid material is pressed into component premix uniformly, feed components and parts by weight are as follows: lactide 100
Part,
0.4 part of antioxidant, 0.3 part of catalyst, 0.3 part of lubricant；
Pre- mixed material is at the uniform velocity added to extrusion machine inlet under logical nitrogen protection, while being vacuumized in exhaust ports,
Screw speed is controlled in 120r/min, and material is in double screw extruder after 15 hours polymerization reactions, and product is through metering pump
It squeezes out, is cooled to solid-state in air.Extrusion temperature is successively are as follows: and 150-160 DEG C, 165-175 DEG C, 175-185 DEG C, 185-190
DEG C, 180-185 DEG C, 210-220 DEG C of die head temperature.
Resulting poly-lactic acid products number-average molecular weight is 5.2 × 105。
4 comparative experiments of embodiment
Lactide, the catalyst of 1 mean quality of Example, using traditional lactide ring-opening polymerisation technique synthesizing polylactic acid
Lactide is added in three-necked flask together with catalyst, heated under vacuum reacts 24 hours, after reaction will
Product is dissolved in chloroform, injects in anhydrous methanol settle until completely dissolved, cotton-shaped sediment is taken out, drying is placed in
40 DEG C vacuum drying 12 hours, obtain product polylactic acid in case.
Resulting poly-lactic acid products number-average molecular weight is 4.1 × 104。
5 comparative experiments of embodiment
Lactide, the catalyst of 2 mean quality of Example, using traditional lactide ring-opening polymerisation technique synthesizing polylactic acid
Lactide is added in three-necked flask together with catalyst, heated under vacuum reacts 24 hours, after reaction will
Product is dissolved in chloroform, injects in anhydrous methanol settle until completely dissolved, cotton-shaped sediment is taken out, drying is placed in
40 DEG C vacuum drying 12 hours, obtain product polylactic acid in case.
Resulting poly-lactic acid products number-average molecular weight is 6.8 × 104。
6 comparative experiments of embodiment
Lactide, the catalyst of 3 mean quality of Example, using traditional lactide ring-opening polymerisation technique synthesizing polylactic acid
Lactide is added in three-necked flask together with catalyst, heated under vacuum reacts 24 hours, after reaction will
Product is dissolved in chloroform, injects in anhydrous methanol settle until completely dissolved, cotton-shaped sediment is taken out, drying is placed in
40 DEG C vacuum drying 12 hours, obtain product polylactic acid in case.
Resulting poly-lactic acid products number-average molecular weight is 5.9 × 104。
Claims (8)
1. a kind of method for preparing poly-lactic acid in high molecular weight by double screw extruder, it is characterised in that the poly-lactic acid material
Including the composition calculated by weight as follows:
100 parts of lactide；
0.2-0.4 parts of antioxidant；
0.1-0.3 parts of catalyst；
0.1-0.3 parts of lubricant.
2. a kind of poly-lactic acid in high molecular weight material according to claim 1 and preparation method thereof, it is characterised in that described
Lactide be self-designed L-lactide.
3. a kind of poly-lactic acid in high molecular weight material according to claim 1 and preparation method thereof, it is characterised in that described
Antioxidant be antioxidant 1010, irgasfos 168, one or more of antioxidant 626 and antioxidant 1098.
4. a kind of poly-lactic acid in high molecular weight material according to claim 1 and preparation method thereof, it is characterised in that described
Catalyst be stannous octoate, in zinc oxide, one kind of stannous chloride.
5. a kind of poly-lactic acid in high molecular weight material according to claim 1 and preparation method thereof, it is characterised in that described
Lubricant be stearic acid, glycerol, paraffin, epoxidized soybean oil, one or more of stearmide.
6. a kind of poly-lactic acid in high molecular weight material according to claim 1 and preparation method thereof, it is characterised in that described
Processing reaction process be to prepare poly-lactic acid material using double screw extruder as reactor.
7. a kind of poly-lactic acid in high molecular weight material according to claim 1 and preparation method thereof, it is characterised in that described
Specific experiment steps are as follows:
L- lactide, catalyst and antioxidant are uniformly mixed and are added to extrusion machine inlet, and logical nitrogen protection, is vented simultaneously
Mouth vacuumizes；When lactide ring-opening polymerisation, screw speed is controlled in 100-120r/min, and polymer is squeezed out through metering pump, is squeezed out
Temperature is successively are as follows: and 150-160 DEG C, 165-175 DEG C, 175-185 DEG C, 185-190 DEG C, 180-185 DEG C, die head temperature 210-220
℃。
8. a kind of poly-lactic acid in high molecular weight material according to claim 1 and preparation method thereof, it is characterised in that described
The lactide polymerization reaction time in double screw extruder be 15 hours.
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| CN201811068025.XA CN109280156A (en) | 2018-09-13 | 2018-09-13 | A method of poly-lactic acid in high molecular weight is prepared by double screw extruder |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11192079B1 (en) | 2020-06-08 | 2021-12-07 | Nutrition & Health Research Institute, COFCO Corporation | Air-isolated continuous feeding system for synthesizing polylactic acid from lactide and feeding method thereof |
| CN113801303A (en) * | 2021-10-27 | 2021-12-17 | 北京工商大学 | Method and device for preparing polylactic acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557854A (en) * | 2004-01-16 | 2004-12-29 | 成都新柯力化工科技有限公司 | Process for preparing poly-lacti acid |
| CN105694017A (en) * | 2014-11-28 | 2016-06-22 | 黑龙江鑫达企业集团有限公司 | Twin-screw reactive extrusion method for preparing polylactic acid by ring-opening polymerization |
| CN106700040A (en) * | 2015-08-21 | 2017-05-24 | 黑龙江鑫达企业集团有限公司 | Method for preparing polylactic acid through twin screw reactive extrusion method and ring open polymerization method |
| 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 |
-
2018
- 2018-09-13 CN CN201811068025.XA patent/CN109280156A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557854A (en) * | 2004-01-16 | 2004-12-29 | 成都新柯力化工科技有限公司 | Process for preparing poly-lacti acid |
| CN105694017A (en) * | 2014-11-28 | 2016-06-22 | 黑龙江鑫达企业集团有限公司 | Twin-screw reactive extrusion method for preparing polylactic acid by ring-opening polymerization |
| CN106700040A (en) * | 2015-08-21 | 2017-05-24 | 黑龙江鑫达企业集团有限公司 | Method for preparing polylactic acid through twin screw reactive extrusion method and ring open polymerization method |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11192079B1 (en) | 2020-06-08 | 2021-12-07 | Nutrition & Health Research Institute, COFCO Corporation | Air-isolated continuous feeding system for synthesizing polylactic acid from lactide and feeding method thereof |
| CN113801303A (en) * | 2021-10-27 | 2021-12-17 | 北京工商大学 | Method and device for preparing polylactic acid |
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