CN102627754A - Method for preparing flexible polylactic acid copolymer - Google Patents
Method for preparing flexible polylactic acid copolymer Download PDFInfo
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- CN102627754A CN102627754A CN2012101210084A CN201210121008A CN102627754A CN 102627754 A CN102627754 A CN 102627754A CN 2012101210084 A CN2012101210084 A CN 2012101210084A CN 201210121008 A CN201210121008 A CN 201210121008A CN 102627754 A CN102627754 A CN 102627754A
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Abstract
The invention discloses a method for preparing a flexible polylactic acid copolymer, belonging to the field of high polymer materials. Raw materials for preparing the flexible polylactic acid copolymer comprise lactide, poly(epsilon-caprolactone) and epoxidized soybean oil. The preparation process comprises the steps of: (1) carrying out a drying treatment on the lactide and the poly(epsilon-caprolactone); (2) adding the raw materials into a reactor; (3) adding a catalyst according to a certain weight ratio; (4) pumping out air in the reactor by a vacuum pump and adding high purity nitrogen; (5) heating according to a certain law; (6) adding the epoxidized soybean oil according to the ratio of the raw materials when the viscosity of the reactant reaches about 200,000 cps; (7) reacting continuously until the viscosity of the reactant does not obviously rise, and ending the reaction; (8) carrying out such treatments as devolatilizing, pelleting, and drying to obtain finished products. The flexible polylactic acid copolymer resin prepared by the method of the invention has the advantages of high tensile strength and elongation at break, low production cost, and biodegradability.
Description
Technical field
The invention belongs to polymeric material field, relate to the preparation method of poly-lactic acid in high molecular weight multipolymer.
Background technology
Over nearest 100 years, with the technical development of this macromolecular material, grow out of nothing and expand from small to large for plastics industry, and global plastics consumption is also more and more.According to statistics; 2011, the usage quantity of global plastics reached nearly 200,000,000 tons scale, but the plastics develop rapidly time; Also brought two serious problems: 1, a large amount of plastic refuse has brought to environment and has been difficult to bear pollution, the white pollution problems puzzlement whole world.2, plastic prod has produced a large amount of Carbon emissions in the process of production and discarded aftertreatment.
POLYACTIC ACID is the biological plastics that tool business development is worth, and at present, nearly 90% is POLYACTIC ACID in the biological plastics.The great market demand causes countries in the world to fall over each other research and development, investment, has quickened its commercialization process, and undoubtedly, the POLYACTIC ACID industry is a tool high development and the strategic industry that concerns environmental protection, reduction of discharging.
POLYACTIC ACID has superior physical property and biocompatibility, but that common POLYACTIC ACID also exists elongation at break is low, and the defective that toughness is relatively poor has influenced it in the have relatively high expectations application in field of snappinesies such as film, sheet material.
Summary of the invention
The present invention provides a kind of preparation method of flexible polylactic acid multipolymer; The objective of the invention is to have high tensile, elongation at break, lower production cost, biodegradable flexible polylactic acid copolymer resin for a kind of multipolymer that is formed by rac-Lactide, poly epsilon caprolactone lactone, epoxy soybean oil is provided.
For addressing the above problem, the present invention adopts following technical scheme: a kind of preparation method of flexible polylactic acid multipolymer, and its raw material integral part is: rac-Lactide, poly epsilon caprolactone lactone, epoxy soybean oil; The parts by weight of each feed composition are respectively:
Rac-Lactide 40-90 part
Poly epsilon caprolactone lactone 10-30 part
Epoxy soybean oil 0-10 part
Its production stage is:
(1), rac-Lactide and poly epsilon caprolactone lactone are carried out drying treatment; Rac-Lactide exsiccant program is: material is added in the vacuum rake dryer, and the equipment Heating temperature is set at 70 ℃, and vacuum tightness is set at absolute pressure≤5000Pa, and the water cut of material reaches≤200PPM, is dry the end; Poly epsilon caprolactone lactone drying program is: material is added in the vacuum rake dryer, and the equipment Heating temperature is set at 40 ℃, and vacuum tightness is set at absolute pressure≤5000Pa, and the water cut of material reaches≤200PPM, is dry the end.
(2), take by weighing rac-Lactide and poly epsilon caprolactone lactone, add in the reaction kettle according to the weight ratio of raw material row;
(3), add catalyzer according to certain part by weight;
(4), utilize vacuum pump to extract the air in the reaction kettle out, and add high pure nitrogen, 2 times so repeatedly, keep the nitrogen atmosphere in the reaction kettle; Keep slight positive pressure in this process reaction still, be generally+0.01～0.03MPA, twice inflation thoroughly replaced for the air in the reaction kettle repeatedly.
(5), heat up according to certain rules; Heat-processed is that program mode heats up, and device temperature keeps 120 ℃, treat that material melts fully after; When temperature of charge between 130～140 ℃ of times, keep the speed of 0.2 ℃/Min to heat up, when temperature of charge between 140～150 ℃ of times; Keep the speed of 0.1 ℃/Min to heat up; When temperature of charge >=150, keep the speed of 0.3 ℃/Min to heat up, until discharging.
(6), when being reacted to viscosity and reaching the 200000 cps left and right sides, add epoxy soybean oil according to material rate;
(7), continue reaction, no longer obviously rises until the viscosity of reaction mass, finish to react, carry out discharging;
(8), carry out devolatilization, granulation, drying treatment, can obtain finished product, a kind of copolymer of poly lactic acid of flexibility.
Further, the preparation method of a kind of flexible polylactic acid multipolymer of the present invention also has following characteristics: described rac-Lactide is a levorotatory lactide, dextrorotation rac-Lactide, outer Xiao Xuan rac-Lactide, a kind of in the interior Xiao Xuan rac-Lactide or several mixture.
The content requirement of rac-Lactide is higher than 99%, and water content requires to be lower than 0.1%.
Described poly epsilon caprolactone lactone, weight-average molecular weight is between 5000～10000.
Described epoxy soybean oil, oxirane value >=6.0%.
Rac-Lactide open loop and PCL, the catalyzer that epoxy soybean oil forms copolyreaction is a phosphorous acid dialkyl ester.
Catalyst consumption is equivalent to rac-Lactide open loop and PCL, and epoxy soybean oil forms 0.02%～2.0% of multipolymer gross weight.
Rac-Lactide open loop and PCL, epoxy soybean oil forms the PCL that is adopted in the copolyreaction, and weight-average molecular weight is 10000～100000.
The present invention is a polymerization single polymerization monomer with rac-Lactide, PCL, epoxy soybean oil, under the condition that catalyzer exists, carries out polyreaction, and its temperature of reaction is 130～180 ℃, and its reaction pressure is-0.08～0.01MPA.
Among the present invention, described reaction kettle is a polymeric material field reaction kettle in general sense, and the requirement that can adapt to the mass polymerization high-viscosity material gets final product.The HV here refers to 2,000,000 cps.
The present invention is a raw material with rac-Lactide, poly epsilon caprolactone lactone, epoxy soybean oil; Under the situation of catalyzer, high temperature and protection of inert gas, carry out ring-opening polymerization; Can obtain the flexible polylactic acid multipolymer, this polymkeric substance can 100% biological degradation, and biocompatibility is better; Index such as tensile strength and elongation at break all far surpasses pure material POLYACTIC ACID, can be used as flexible higher Application Areas such as film, sheet material.
The copolymer of poly lactic acid that makes according to the inventive method has the molecular weight height, Young's modulus is good, has higher intensity and the elongation at break of drawing high.Be generally particulate state.
Embodiment
With illustrated embodiments the present invention is done detailed explanation below.
Through embodiment technical scheme of the present invention is done further specifying below, but the present invention is not limited to these embodiment.
Embodiment 1:
(1), takes by weighing 90 parts of rac-Lactides, 10 parts of PCL resins, 0 part of epoxy soybean oil; Respectively preceding two kinds of raw materials are carried out drying treatment;
(2) dried rac-Lactide and PCL resin are added in the reaction kettle, add the phosphorous acid dialkyl ester of two kinds of mixture quality per-cents 0.02%;
(3) utilize air in the high pure nitrogen replacement reaction kettle;
(4) open heating unit, material is heated,, carry out stage intensification according to level of response control temperature of charge.
(5) when reactant viscosity no longer obviously rises, finish reaction, discharging, granulation can obtain the copolymer of poly lactic acid of a kind of flexibility of weight-average molecular weight about 220,000.
Embodiment 2:
(1), takes by weighing 80 parts of rac-Lactides, 10 parts of PCL resins, 10 parts of epoxy soybean oils; Respectively preceding two kinds of raw materials are carried out drying treatment;
(2) dried rac-Lactide and PCL resin are added in the reaction kettle, add the phosphorous acid dialkyl ester of two kinds of mixture quality per-cents 0.02%;
(3) utilize air in the high pure nitrogen replacement reaction kettle;
(4) open heating unit, material is heated,, carry out stage intensification according to level of response control temperature of charge.
(5) when material viscosity reaches 200,000 CPS, add 10 parts epoxy soybean oil.Continue to heat up, the control material carries out polyreaction.
(6) when reactant viscosity no longer obviously rises, finish reaction, discharging, granulation can obtain a kind of copolymer of poly lactic acid of flexibility.
Embodiment 3:
(1), takes by weighing 70 parts of rac-Lactides, 20 parts of PCL resins, 10 parts of epoxy soybean oils; Respectively preceding two kinds of raw materials are carried out drying treatment;
(2) dried rac-Lactide and PCL resin are added in the reaction kettle, add the phosphorous acid dialkyl ester of two kinds of mixture quality per-cents 0.02%;
(3) utilize air in the high pure nitrogen replacement reaction kettle;
(4) open heating unit, material is heated,, carry out stage intensification according to level of response control temperature of charge.
(5) when material viscosity reaches 200,000 CPS, add 10 parts epoxy soybean oil.Continue to heat up, the control material carries out polyreaction.
(6) when reactant viscosity no longer obviously rises, finish reaction, discharging, granulation can obtain a kind of copolymer of poly lactic acid of flexibility.
Embodiment 4:
(1), takes by weighing 60 parts of rac-Lactides, 30 parts of PCL resins, 10 parts of epoxy soybean oils; Respectively preceding two kinds of raw materials are carried out drying treatment;
(2) dried rac-Lactide and PCL resin are added in the reaction kettle, add the phosphorous acid dialkyl ester of two kinds of mixture quality per-cents 0.02%;
(3) utilize air in the high pure nitrogen replacement reaction kettle;
(4) open heating unit, material is heated,, carry out stage intensification according to level of response control temperature of charge.
(5) when material viscosity reaches 200,000 CPS, add 10 parts epoxy soybean oil.Continue to heat up, the control material carries out polyreaction.
(6) when reactant viscosity no longer obviously rises, finish reaction, discharging, granulation can obtain a kind of copolymer of poly lactic acid of flexibility.
Embodiment 5:
(1), takes by weighing 60 parts of rac-Lactides, 35 parts of PCL resins, 5 parts of epoxy soybean oils; Respectively preceding two kinds of raw materials are carried out drying treatment;
(2) dried rac-Lactide and PCL resin are added in the reaction kettle, add the phosphorous acid dialkyl ester of two kinds of mixture quality per-cents 0.02%;
(3) utilize air in the high pure nitrogen replacement reaction kettle;
(4) open heating unit, material is heated,, carry out stage intensification according to level of response control temperature of charge.
(5) when material viscosity reaches 200,000 CPS, add 10 parts epoxy soybean oil.Continue to heat up, the control material carries out polyreaction.
(6) when reactant viscosity no longer obviously rises, finish reaction, discharging, granulation can obtain a kind of copolymer of poly lactic acid of flexibility.
Embodiment 6:
(1), takes by weighing 70 parts of rac-Lactides, 25 parts of PCL resins, 5 parts of epoxy soybean oils; Respectively preceding two kinds of raw materials are carried out drying treatment;
(2) dried rac-Lactide and PCL resin are added in the reaction kettle, add the phosphorous acid dialkyl ester of two kinds of mixture quality per-cents 0.02%;
(3) utilize air in the high pure nitrogen replacement reaction kettle;
(4) open heating unit, material is heated,, carry out stage intensification according to level of response control temperature of charge.
(5) when material viscosity reaches 200,000 CPS, add 10 parts epoxy soybean oil.Continue to heat up, the control material carries out polyreaction.
(6) when material viscosity reaches 1,500,000 CPS, finish reaction, discharging, granulation can obtain a kind of copolymer of poly lactic acid of flexibility.
Embodiment 7:
(1), takes by weighing 80 parts of rac-Lactides, 15 parts of PCL resins, 5 parts of epoxy soybean oils; Respectively preceding two kinds of raw materials are carried out drying treatment;
(2) dried rac-Lactide and PCL resin are added in the reaction kettle, add the phosphorous acid dialkyl ester of two kinds of mixture quality per-cents 0.02%;
(3) utilize air in the high pure nitrogen replacement reaction kettle;
(4) open heating unit, material is heated,, carry out stage intensification according to level of response control temperature of charge.
(5) when material viscosity reaches 200,000 CPS, add 10 parts epoxy soybean oil.Continue to heat up, the control material carries out polyreaction.
(6) when material viscosity reaches 1,500,000 CPS, finish reaction, discharging, granulation can obtain a kind of copolymer of poly lactic acid of flexibility.
The performance of the prepared material of table 1: embodiment 1～7 each component
Can find out that from last table along with the per-cent of PCL in material increases, the gentle tensile strength of material presents downtrending, but elongation at break presents ascendant trend.Epoxy soybean oil then can improve the thermostability of copolymer of poly lactic acid, and helps the carrying out of ring-opening polymerization.
Can know from above-mentioned instance, the invention discloses a kind of flexible polylactic acid multipolymer, compare with pure PLA resin; Can increase substantially the elongation at break of material; Flexible obviously raising can be applicable to flexible demanding occasions such as film, sheet material, is with a wide range of applications and market outlook.
What should explain at last is: obviously, the foregoing description only be for clearly the present invention is described and is done for example, and be not qualification to embodiment.For the those of ordinary skill in affiliated field, on the basis of above-mentioned explanation, can also make other multi-form variation or change.Here need not also can't give exhaustive to all embodiments.And conspicuous variation of being amplified out thus or change still are among protection scope of the present invention.
Claims (9)
1. the preparation method of a flexible polylactic acid multipolymer is characterized in that, its raw material integral part is: rac-Lactide, poly epsilon caprolactone lactone, epoxy soybean oil; The parts by weight of each feed composition are respectively:
Rac-Lactide 40-90 part
Poly epsilon caprolactone lactone 10-30 part
Epoxy soybean oil 0-10 part
Its production stage is:
(1), rac-Lactide and poly epsilon caprolactone lactone are carried out drying treatment;
(2), take by weighing rac-Lactide and poly epsilon caprolactone lactone, add in the reaction kettle according to the weight ratio of raw material row;
(3), add catalyzer according to certain part by weight;
(4), utilize vacuum pump to extract the air in the reaction kettle out, and add high pure nitrogen, 2 times so repeatedly, keep the nitrogen atmosphere in the reaction kettle;
(5), heat up according to certain rules;
(6), when being reacted to viscosity and reaching the 200000 cps left and right sides, add epoxy soybean oil according to material rate;
(7), continue reaction, no longer obviously rises until the viscosity of reaction mass, finish to react, carry out discharging;
(8), carry out devolatilization, granulation, drying treatment, can obtain finished product, a kind of copolymer of poly lactic acid of flexibility.
2. a kind of according to claim 1 preparation method of flexible polylactic acid multipolymer is characterized in that, described rac-Lactide is a levorotatory lactide, dextrorotation rac-Lactide, outer Xiao Xuan rac-Lactide, a kind of in the interior Xiao Xuan rac-Lactide or several mixture.
3. like the preparation method of the said a kind of flexible polylactic acid multipolymer of claim 2, it is characterized in that the content requirement of rac-Lactide is higher than 99%, water content requires to be lower than 0.1%.
4. a kind of according to claim 1 preparation method of flexible polylactic acid multipolymer is characterized in that, described poly epsilon caprolactone lactone, and weight-average molecular weight is between 5000～10000.
5. a kind of according to claim 1 preparation method of flexible polylactic acid multipolymer is characterized in that, described epoxy soybean oil, oxirane value >=6.0%.
6. a kind of according to claim 1 preparation method of flexible polylactic acid multipolymer is characterized in that, rac-Lactide open loop and PCL, and the catalyzer that epoxy soybean oil forms copolyreaction is a phosphorous acid dialkyl ester.
7. like the preparation method of the said a kind of flexible polylactic acid multipolymer of claim 6, it is characterized in that catalyst consumption is equivalent to rac-Lactide open loop and PCL, epoxy soybean oil forms 0.02%～2.0% of multipolymer gross weight.
8. a kind of according to claim 1 preparation method of flexible polylactic acid multipolymer is characterized in that, rac-Lactide open loop and PCL, and epoxy soybean oil forms the PCL that is adopted in the copolyreaction, and weight-average molecular weight is 10000～100000.
9. a kind of according to claim 1 preparation method of flexible polylactic acid multipolymer; It is characterized in that, be polymerization single polymerization monomer with rac-Lactide, PCL, epoxy soybean oil, under the condition that catalyzer exists, carries out polyreaction; Its temperature of reaction is 130～180 ℃, and its reaction pressure is-0.08～0.01MPA.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435981A (en) * | 2013-08-06 | 2013-12-11 | 东莞市鑫海环保材料有限公司 | Preparation method of full biodegradation film |
| CN112898750A (en) * | 2021-01-26 | 2021-06-04 | 嘉兴学院 | Full-biodegradable toughened polylactic acid composite material and preparation method thereof |
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| CN101186687A (en) * | 2007-12-04 | 2008-05-28 | 武汉大学深圳研究院 | Method for preparing polylactic acid by lactide open loop polymerization reaction |
| CN101538359A (en) * | 2009-04-10 | 2009-09-23 | 重庆大学 | Method for preparing high molecular weight branched polylactic acid by molten polymerization |
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- 2012-04-24 CN CN2012101210084A patent/CN102627754A/en active Pending
Patent Citations (4)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103435981A (en) * | 2013-08-06 | 2013-12-11 | 东莞市鑫海环保材料有限公司 | Preparation method of full biodegradation film |
| CN112898750A (en) * | 2021-01-26 | 2021-06-04 | 嘉兴学院 | Full-biodegradable toughened polylactic acid composite material and preparation method thereof |
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Application publication date: 20120808 |