CN102924695A - Method for preparing three-dimensional block polylactic acid at high efficiency - Google Patents
Method for preparing three-dimensional block polylactic acid at high efficiency Download PDFInfo
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- CN102924695A CN102924695A CN2012103555328A CN201210355532A CN102924695A CN 102924695 A CN102924695 A CN 102924695A CN 2012103555328 A CN2012103555328 A CN 2012103555328A CN 201210355532 A CN201210355532 A CN 201210355532A CN 102924695 A CN102924695 A CN 102924695A
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Abstract
The invention provides a method for preparing three-dimensional block polylactic acid at high efficiency. The method is characterized by comprising the following steps of: (1) pre-polymerizing: adding polymerization-stage D type (or L type) lactide, a catalyst and an initiator into a polymerization reactor, heating to the first reaction temperature of 160-200DEG C under the protection of inert gas, reacting for 0-1hour after a set temperature is achieved, cooling to the second reaction temperature of 100-150 DEG C, and reacting for 0.5-5hours to obtain a prepolymer; and (2) carrying out block copolymerization: taking the prepolymer prepared by the step (1) as a raw material, adding the polymerization-stage L type (or D type) lactide into the polymerization reactor, wherein the mass ratio is (1:9)-(3:7), the reaction temperature is 190-230DEG C under the protection of inert gas, and the reaction time is 0.5-5hours after the set temperature is achieved, so that the three-dimensional block polylactic acid can be obtained.
Description
Technical field
The invention belongs to the organic polymer material field, relate to a kind of preparation method of poly(lactic acid), relate in particular to a kind of efficient method for preparing the stereoblock poly(lactic acid).
Background technology
Poly(lactic acid) (PLA) is a kind of biodegradable polymer of producing take renewable resourcess such as W-Gums as starting raw material, its preparation and application be one derive from renewable resources, work-ing life and finish after the degraded product back to nature, participate in a desirable ecological circulation of going in the process of biomass resource regeneration, belong to the part of nature carbon cycle.The thermal plasticity high polymer that the physical and mechanical propertiess such as poly(lactic acid) and polystyrene, polyester are close, has good Physical and mechanical properties, and good processability, can use conventional methods forming process, also can with general-purpose plastics blend or copolymerization, all have a good application prospect in fields such as agricultural, wrapping material, daily life, clothes and bio-medical materials, thereby poly(lactic acid) becomes Recent study and develops most active biodegradable polymer.But the thermotolerance of poly(lactic acid) is relatively relatively poor, and the second-order transition temperature of common poly(lactic acid) is generally at 50～60 ℃, and fusing point will be expanded the application of poly(lactic acid) at 150～170 ℃, must improve its thermotolerance.The problems such as three-dimensional compound poly(lactic acid) fusing point can reach 230 ℃, but owing to its intrinsic characteristic, exists the production rate of three-dimensional composite crystal not high, and processing stability is not strong.Stereoblock poly(lactic acid) fusing point can arrive about 210 ℃, possess machinery and thermal characteristics near polybutylene terephthalate (PBT), and the production rate of three-dimensional composite crystal (sc) can reach 100%, and processing stability is also better, is the environment-friendly materials of new generation that have development potentiality.
Among the patent CN 101522755A, a kind of preparation method of poly(lactic acid) is disclosed.Namely adopt ring-opening polymerization to obtain the first poly(lactic acid), and under molten state, remove residual rac-Lactide, then the ring-opening polymerization that causes the second rac-Lactide in the presence of the first poly(lactic acid) obtains the second poly(lactic acid) (being the stereoblock poly(lactic acid)), can obtain the stereoblock poly(lactic acid) of molecular weight more than 150,000, and have preferably sc production rate and stability.But owing to there being the step of removing residual lactide in the first poly(lactic acid), cause operation too complicated, and in the situation that do not add the catalyst deactivation agent and carry out removing of rac-Lactide and can not obtain good effect, because the reaction of polymerization and depolymerization still can be carried out under the catalysis of remaining catalyzer, thereby reaches molecular balance.Among the patent CN 101595157A, a kind of preparation method of polylactic-acid block copolymer is disclosed.Namely at first adopt the ring-opening polymerization of D-rac-Lactide to prepare low-molecular-weight poly-D-ALPHA-Hydroxypropionic acid, then remove residual D-rac-Lactide through the decompression method, further carry out ring-opening polymerization with the L-rac-Lactide and obtain polylactic-acid block copolymer (being the stereoblock poly(lactic acid)), can obtain molecular weight more than 100,000, the higher and more stable polylactic-acid block copolymer of three-dimensional composite crystal production rate.But owing to there being the step of removing residual lactide, cause operation too complicated, the operating time is long, is unfavorable for industrialization.
Summary of the invention
The objective of the invention is to overcome the existing not high difficult problem of three-dimensional compound poly(lactic acid) preparation process preparation process production efficiency, disclose a kind of efficient method for preparing the stereoblock poly(lactic acid), to satisfy the needs of producing and using.
The invention discloses a kind of efficient method for preparing the stereoblock poly(lactic acid), it is characterized in that comprising the steps:
(1) pre-polymerization:
D type (or L-type) rac-Lactide and catalyzer, the initiator of polymerization-grade are added polymerization reactor; under protection of inert gas; be warming up to the first temperature of reaction of 160～200 ℃; reach design temperature afterreaction 0～1h; be cooled to subsequently the second temperature of reaction of 100～150 ℃; reaction 0.5～5h obtains prepolymer.
(2) block copolymerization:
The prepolymer that step (1) is made is as raw material; add polymerization reactor with L-type (or the D type) rac-Lactide of polymerization-grade; mass ratio is 1: 9～3: 7; under protection of inert gas; 190～230 ℃ of temperature of reaction; after reaching design temperature, the reaction times is 0.5～5h, obtains the stereoblock poly(lactic acid).
It is characterized in that in the step (1) optical purity of described D type (or L-type) rac-Lactide 〉=99%.
It is characterized in that in the step (1), described the first temperature of reaction is preferably 170～190 ℃.
It is characterized in that in the step (1), described the second temperature of reaction is preferably 120～140 ℃.
It is characterized in that in the step (2), described temperature of reaction is preferably 195～215 ℃.
Beneficial effect provided by the invention is:
(1) avoided the operation of polymkeric substance removal residual lactide in the pilot process, production technique is simple, easy to operate.
(2) owing to not removing the loss of rac-Lactide, final productive rate is high, and cost is low, is easy to realize that industrialization produces continuously.
Description of drawings
Fig. 1 is the DSC curve of stereoblock poly(lactic acid) SB4.Fig. 2 is the DSC curve of stereoblock poly(lactic acid) C1.
Embodiment
1, characterizing method
The molecular weight of poly(lactic acid) adopts gel permeation chromatography (GPC) to measure, condition is: U.S. Waters company 1515 type gel permeation chromatographs, Waters 2414 differential detectors, Waters 1515Isocratic HPLC pump, ETL LISTED-81437 column oven, the polystyrene packing, the residual level of farming chloroform is moving phase, flow velocity is 1.0mL/min, take the chloroform that contains the 10vol% hexafluoroisopropanol as solvent, sample ligand is set to the solution of 0.3wt%, sample size is 100 μ L, 35 ℃ of column temperatures, 35 ℃ of detector temperatures.
The spectral analysis of the nuclear magnetic resonance of poly(lactic acid) adopts the German BRUKER ADVANCE III of company type nuclear magnetic resonance spectrometer to measure the structure of polymerisate.With the deuterium that contains the 10vol% hexafluoroisopropanol for trichloromethane as solvent, carbon spectrum resonant frequency is 100MHz, the hydrogen spectrum is 400MHz, tests under 25 ℃ of conditions of room temperature.
The thermal characteristics of poly(lactic acid) adopts the anti-DSC 200F3 of the company type differential scanning calorimeter of speeding of Germany, and under the 50mL/min nitrogen protection, 10 ℃/min tests with temperature rise rate.
2, experimental technique
Preparation example 1
D type rac-Lactide 20.0g and 0.004g stannous octoate, the 0.18g lauryl alcohol of polymerization-grade are added polymerization reactor, under nitrogen protection, be warming up to the first temperature of reaction of 180 ℃; reach design temperature afterreaction 4h; be cooled to subsequently the second temperature of reaction of 130 ℃, reaction 2h obtains prepolymer P1.
Preparation example 2
D type rac-Lactide 20.0g and 0.004g stannous octoate, the 0.10g lauryl alcohol of polymerization-grade are added polymerization reactor, under nitrogen protection, be warming up to the first temperature of reaction of 190 ℃; reach design temperature afterreaction 0h; be cooled to subsequently the second temperature of reaction of 100 ℃, reaction 5h obtains prepolymer P2.
Preparation example 3
D type rac-Lactide 20.0g and 0.004g stannous octoate, the 0.18g lauryl alcohol of polymerization-grade are added polymerization reactor, under nitrogen protection, be warming up to the first temperature of reaction of 180 ℃, reach design temperature afterreaction 0h, obtain prepolymer P3.
Preparation example 4
D type rac-Lactide 20.0g and 0.004g stannous octoate, the 0.10g lauryl alcohol of polymerization-grade are added polymerization reactor, under nitrogen protection, be warming up to the first temperature of reaction of 180 ℃, reach design temperature afterreaction 1h, obtain prepolymer P4.
Embodiment 1
The prepolymer P1 of 5.1g as raw material, is added polymerization reactor with the L-type rac-Lactide 20.2g of polymerization-grade, under nitrogen protection, 200 ℃ of temperature of reaction, reach design temperature after, the reaction times is 2h, obtains stereoblock poly(lactic acid) SB1.
Embodiment 2
The prepolymer P1 of 5.0g as raw material, is added polymerization reactor with the L-type rac-Lactide 20.0g of polymerization-grade, under nitrogen protection, 220 ℃ of temperature of reaction, reach design temperature after, the reaction times is 1h, obtains stereoblock poly(lactic acid) SB2.
Embodiment 3
The prepolymer P2 of 6.0g as raw material, is added polymerization reactor with the L-type rac-Lactide 14.0g of polymerization-grade, under nitrogen protection, 220 ℃ of temperature of reaction, reach design temperature after, the reaction times is 0.5h, obtains stereoblock poly(lactic acid) SB3.
Embodiment 4
The prepolymer P2 of 5.0g as raw material, is added polymerization reactor with the L-type rac-Lactide 20.0g of polymerization-grade, under nitrogen protection, 200 ℃ of temperature of reaction, reach design temperature after, the reaction times is 1h, obtains stereoblock poly(lactic acid) SB4.
Comparative example 1
The prepolymer P3 of 5.0g as raw material, is added polymerization reactor with the L-type rac-Lactide 20.0g of polymerization-grade, under nitrogen protection, 200 ℃ of temperature of reaction, reach design temperature after, the reaction times is 1h, obtains stereoblock poly(lactic acid) C1.
Comparative example 2
The prepolymer P4 of 5.0g as raw material, is added polymerization reactor with the L-type rac-Lactide 20.0g of polymerization-grade, under nitrogen protection, 200 ℃ of temperature of reaction, reach design temperature after, the reaction times is 1h, obtains stereoblock poly(lactic acid) C3.
Comparative example 3
The prepolymer P3 of 6.0g as raw material, is added polymerization reactor with the L-type rac-Lactide 14.0g of polymerization-grade, under nitrogen protection, 220 ℃ of temperature of reaction, reach design temperature after, the reaction times is 0.5h, obtains stereoblock poly(lactic acid) C2.
3, result and discussion
The resulting product of above preparation example, embodiment and comparative example is characterized, and data as shown in Table 1 and Table 2.
The residual comparison of rac-Lactide of table 1 preparation example product
The sc production rate of table 2 embodiment and comparative example product relatively
Δ H wherein
HcBe the melting enthalpy of homogeneous phase poly(lactic acid), wherein Δ H
ScBe the melting enthalpy of stereoblock poly(lactic acid), T
MscBe the fusing point of stereoblock poly(lactic acid), the sc production rate adopts following formula to obtain:
The production rate of sc has larger impact to the thermotolerance of product, and the sc production rate is higher, and it is heat-resisting better.Can find out that from table 2 and Fig. 1, Fig. 2 the sc production rate of the stereoblock poly(lactic acid) that embodiment prepares all reaches 100%, and comparative example all can not get the stereoblock poly(lactic acid) of 100% production rate.
Table 1 has shown weight-average molecular weight and the rac-Lactide residual rate of the prepolymer that preparation example obtains, the rac-Lactide residual rate of the resulting prepolymer of the solution of the present invention is described far below common preparation method, thereby has avoided removing this step of the residual rac-Lactide of prepolymer.Thereby adopt the present invention can improve the production efficiency of preparation stereoblock poly(lactic acid), be conducive to industrialization.
Claims (5)
1. a method that efficiently prepares the stereoblock poly(lactic acid) is characterized in that comprising the steps:
(1) pre-polymerization:
D type (or L-type) rac-Lactide and catalyzer, the initiator of polymerization-grade are added polymerization reactor; under protection of inert gas; be warming up to the first temperature of reaction of 160～200 ℃; reach design temperature afterreaction 0～1h; be cooled to subsequently the second temperature of reaction of 100～150 ℃; reaction 0.5～5h obtains prepolymer.
(2) block copolymerization:
The prepolymer that step (1) is made is as raw material; add polymerization reactor with L-type (or the D type) rac-Lactide of polymerization-grade; mass ratio is 1: 9～3: 7; under protection of inert gas; 190～230 ℃ of temperature of reaction; after reaching design temperature, the reaction times is 0.5～5h, obtains the stereoblock poly(lactic acid).
2. the high efficiency method of described preparation stereoblock poly(lactic acid) according to claim 1 is characterized in that in the step (1) optical purity of described D type (or L-type) rac-Lactide 〉=99%.
3. the high efficiency method of described preparation stereoblock poly(lactic acid) according to claim 2 is characterized in that in the step (1), described the first temperature of reaction is preferably 170～190 ℃.
4. the high efficiency method of described preparation stereoblock poly(lactic acid) according to claim 1 is characterized in that in the step (1), described the second temperature of reaction is preferably 120～140 ℃.
5. the high efficiency method of described preparation stereoblock poly(lactic acid) according to claim 1 is characterized in that in the step (2), described temperature of reaction is preferably 195～215 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106715524A (en) * | 2014-08-19 | 2017-05-24 | 荷兰普拉克公司 | Lactide block copolymer and method of preparation |
| WO2021217299A1 (en) * | 2020-04-26 | 2021-11-04 | 万华化学(四川)有限公司 | Production method for preparing polylactic acid by means of ring-opening polymerization method, and prepolymer mixture and polylactic acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1412220A (en) * | 2002-07-12 | 2003-04-23 | 天津大学 | Preparation method of polyethylene-b-polylactic acid amphiphilic diblock copolymer |
| CN101747494A (en) * | 2008-12-02 | 2010-06-23 | 东丽纤维研究所（中国）有限公司 | Method for preparing bi-block copolymer with controllable molecular weight |
| WO2012029393A1 (en) * | 2010-08-31 | 2012-03-08 | 東レ株式会社 | Polylactic acid block copolymer |
-
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- 2012-09-19 CN CN2012103555328A patent/CN102924695A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1412220A (en) * | 2002-07-12 | 2003-04-23 | 天津大学 | Preparation method of polyethylene-b-polylactic acid amphiphilic diblock copolymer |
| CN101747494A (en) * | 2008-12-02 | 2010-06-23 | 东丽纤维研究所（中国）有限公司 | Method for preparing bi-block copolymer with controllable molecular weight |
| WO2012029393A1 (en) * | 2010-08-31 | 2012-03-08 | 東レ株式会社 | Polylactic acid block copolymer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106715524A (en) * | 2014-08-19 | 2017-05-24 | 荷兰普拉克公司 | Lactide block copolymer and method of preparation |
| CN106715524B (en) * | 2014-08-19 | 2019-08-02 | 荷兰普拉克公司 | Lactide block copolymer and preparation method thereof |
| WO2021217299A1 (en) * | 2020-04-26 | 2021-11-04 | 万华化学(四川)有限公司 | Production method for preparing polylactic acid by means of ring-opening polymerization method, and prepolymer mixture and polylactic acid |
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Application publication date: 20130213 |