CN101200533B - Polylactide polymers for plasticizer and production method - Google Patents
Polylactide polymers for plasticizer and production method Download PDFInfo
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- CN101200533B CN101200533B CN2006101614453A CN200610161445A CN101200533B CN 101200533 B CN101200533 B CN 101200533B CN 2006101614453 A CN2006101614453 A CN 2006101614453A CN 200610161445 A CN200610161445 A CN 200610161445A CN 101200533 B CN101200533 B CN 101200533B
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Abstract
The present invention discloses a polylactic polymer of plastic agent and the production method. The present invention takes an iron compound as the catalyst and adopts lactide and polyamine alkyl ether polymer to obtain the polymer; the structure is PLA-B-PLA; wherein, the structure of B is that: n is 2 to 6 and PLA is polylatex. In using the product provided by the present invention, the plastic agent will not move; the stretching modulus of the film product under the temperature of 23 DEG C can reach 0.1 to 2 GPa.
Description
Technical field:
The present invention relates to polylactic acid base polymer composition, relate to plasticizer in more detail and give polymkeric substance flexibility, toughness.
Technical background:
Along with the consumption of present global plastics is more and more, the problem of two sternnesses has also appearred in the development of plastics thereupon: 1. a large amount of waste plastics imposes very big pressure 2. limited petroleum resources to environment and has beaten alarm bell for the production of plastics.
Poly(lactic acid) (PLA) is easy to be become CO by biological degradation under the adjusting of aerobic and water
2And H
2O, and the raw material of PLA is from annual plant corn, the discovery of PLA has just solved the two big fatefulue problems that plastic industry runs into, so the application of PLA will replace plastics application in some aspects fully like this.
But PLA also has very big difficulty aspect the film being used for: because PLA has very big fragility, if want PLA to be made film and very big toughness is arranged, must improve the toughness of PLA; Must be if want to improve the toughness of PLA by the adjusting of additive.
There are a lot of scholars and expert also to use a lot of additives to improve the toughness of PLA at present, utilize glycerine triethyl and tributyl citrate to come plasticising PLA as Ljungberg etc., but the in use easily continuous cold crystallization of the film that makes like this, force plasticizer migration to arrive the surface of film, the performance that causes film in time prolongation and change rapidly, final flexibility reduces greatly.Yue etc. utilize blend to improve the toughness of PLA, and they study poly(lactic acid) and polyethylene oxide/polyethylene glycol blending, but the performance of blend is not very desirable.Though but the fairly simple performance of the method for blend is difficult to reach the demand of industry.Chengdu Organic Chemistry Inst., Chinese Academy of Sciences has invented with the embedding end multipolymer of triisobutyl aluminium as Preparation of Catalyst high molecular weight polylactic acid and polyether glycol, but the program of being somebody's turn to do will add molecular weight regulator, and the purity requirement to rac-Lactide is higher, particularly the suitable complexity of the processing of moisture.
Summary of the invention:
The polylactic acid base polymer of plasticizer of the present invention can in use not move from poly-lactic acid products, and catalyzer can in use not separated out intoxicating as heavy metal catalyst in the past yet.
The technical solution that the present invention adopts is:
A kind of polylactic acid base polymer of plasticizer is characterized in that: be compound with iron as catalyzer, utilize rac-Lactide with
The polyalkylene ether polymer carries out the polymkeric substance that polymerization makes; Its structure is PLA-B-PLA, and wherein the structure of B is
N is 2～6, and PLA is a poly(lactic acid).
The structure of polyalkylene ether polymer is a linear polymer, is molecular weight at 1500～15000 polyoxyethylene glycol (PEG), polypropylene glycol (PPG) or polytetrahydrofuran (PTMG).The compound of described iron is ferric acetyl acetonade or iron stearate.
A kind of production method of polylactic acid base polymer of plasticizer is characterized in that: with rac-Lactide and structural formula be
The polyalkylene ether polymer, under the condition that catalyzer exists, reaction makes product; Described catalyzer is the compound of iron.
The consumption of polyalkylene ether polymer is to be equivalent to 20%～80% of plasticizer polylactic acid polymer weight.Catalyst consumption be equivalent to plasticizer polylactic acid base polymer weight 0.05～3.0%.
, under nitrogen protection, react then as raw material with PEG-6000, add the deactivator reaction again, slowly vacuumize devolatilization at last and get final product by adding rac-Lactide and catalyzer after the vacuum-drying.
In above method, the molecular weight of the polylactic acid base polymer of the plasticizer that makes is between 7500～16000.The poly(lactic acid) of this plasticizer and polylactic acid blend finally make the poly (lactic acid) composition of plasticity.Tensile modulus can reach 0.1～2GPa when this film was 23 ℃ in temperature.The content of oligopolymer is below 2wt% in the final film.
Compare with technology in the past, beneficial effect of the present invention is:
1. the poly(lactic acid) of the plasticizer that makes of the present invention is the segmented copolymer of PLA and PEG, therefore can from the film product of PLA, not move, so just solve additive in the past and from film product, moved the defective of coming out, thereby solved the problem in work-ing life of PLA film product; 2. because the catalyzer that this experiment is used is the compound of iron, not only the catalyzer price comparison cheap and also in the process of using catalyzer can not separate out, in use separate out toxic heavy metal easily unlike heavy metal catalysts such as Sn in the past and cause the use range of product to be restricted; 3. the poly(lactic acid) plasticizing effect of this plasticizer is relatively good, and the film that makes tensile modulus under 23 ℃ condition can reach 0.1～2GPa.
Embodiment 1:
The preparation of plasticizer polylactic acid polymer:
The PEG-6000 that in the test tube of cleaning that has Tu Zui, adds 58.9g, load onto the coincidence head then, be put in 160 ℃ the silicone oil groove, connect and stir, the speed that stirs is transferred to 17rpm, before PEG dissolving,, about 3 times, under vacuum, react 30 minutes (vacuum tightness approximately is 300Pa) then with nitrogen replacement(metathesis)reaction system repeatedly.Recover normal pressure and add ready 41.1g rac-Lactide, stirring velocity is transferred to 29rpm, and with about 3 bouts of nitrogen replacement reaction system, feed the nitrogen reaction after 10 minutes, add catalyzer ferric acetyl acetonade (0.1mol/ml, 2.5ml, toluene is solvent), feeding nitrogen reacted 2 hours down after continuing displacement 3 bouts, (0.1mol/ml 0.09ml) feeds the following reaction of nitrogen and begins devolatilization after 20 minutes, slowly vacuumizes half an hour to add deactivator phosphoric acid crystallisate again, resulting pressure is about 200Pa, spues at last.The preparation of plasticity polylactic acid base polymer composition:
Taking by weighing plasticizer polylactic acid polymer that this embodiment of 30g prepares mixes with the 70g poly(lactic acid) and adds in the hard test tube; then test tube is put into 210 ℃ silicone oil groove; nitrogen protection was reacted 20 minutes down, and stirring velocity is 29r/min, and final vacuum reaction down got final product in 30 minutes.
Embodiment 2:
Experimentation and condition are identical with embodiment 1, and the amount of catalyzer is 0.1mol/L, 10ml, and toluene is as solvent.
Embodiment 3:
Experimentation is identical with embodiment 1 with condition, and the amount of catalyzer is 1mol/L, 2.5ml, and toluene is as solvent.
Embodiment 4:
Experimentation is identical with embodiment 1 with condition, and the amount of catalyzer is 0.1mol/L, and 1.4ml, toluene are solvent; The amount of PEG-6000 is 13.7g.
Embodiment 5:
Experimentation is identical with embodiment 1 with condition, and the amount of catalyzer is 0.1mol/L, 3.5ml, and toluene is as flux; The amount of PEG-6000 is 95.9g.
Embodiment 6:
Experimentation is identical with embodiment 1 with condition, and catalyzer is an iron stearate, and consumption is 0.1mol/L, 2.5ml, and toluene is as flux; The amount of PEG-6000 is 58.9g.
Embodiment 7:
Process of the test is identical with embodiment 1 with condition, and its plasticizer is PTMG-1800, and consumption is 35.4g, and the consumption of rac-Lactide is 64.6g; Catalyzer is a ferric acetyl acetonade, and consumption is 0.1mol/L, 2.5ml.
Embodiment 8:
Process of the test is identical with embodiment 1 with condition, and its plasticizer is PPG-6000, and consumption is 58.9g, and the consumption of rac-Lactide is 41.1g, and catalyzer is a ferric acetyl acetonade, and consumption is 0.1mol/L, 2.5ml.
Embodiment 9:
With rac-Lactide and molecular weight at 1500～15000 polyoxyethylene glycol (or polypropylene glycol or polytetrahydrofuran) under the condition that catalyzer ferric acetyl acetonade (or iron stearate) exists, reaction makes product; The consumption of polyalkylene ether polymer is 20%～80% (example 20%, 50%, 80%) that is equivalent to plasticizer polylactic acid polymer weight, and catalyst consumption is 0.05～3.0% (example 0.05%, 1.5%, 3%) that is equivalent to the polylactic acid base polymer weight of plasticizer.
Making product structure is PLA-B-PLA, and wherein the structure of B is
N is 2～6 (examples 2,4,6), and PLA is a poly(lactic acid).
Comparative example 1:
Experimentation is identical with embodiment 1 with condition, and catalyzer is 58.9g for the amount for isocaprylic acid aluminium (toluene is as flux for 0.1mol/L, 2.2ml) PEG.
Comparative example 2:
Experimentation is identical with embodiment 1 with condition, and catalyzer is lime acetate (0.1mol/L, 6.2ml, toluene are solvent).
Comparative example 3:
Experimentation is identical with embodiment 1 with condition, and catalyzer is lithium chloride (0.1mol/L, 23ml, toluene are solvent).
The technical indicator of product:
From top form as can be seen, suitable with the technical indicator of the poly(lactic acid) of the plasticizer that makes as catalyzer with Sn with ferric acetyl acetonade as catalyzer.Ferric acetyl acetonade can substitute the catalyzer of Sn fully, and the price of catalyzer is reduced greatly, and does not in use also have separating out of toxic heavy metal.Use ferric acetyl acetonade not only can make the PLA of plasticity like this, and make the widely-used more life-span of its range of application also become longer as catalyzer.
The method of evaluating performance of product:
1.COOH Determination on content adopts the optics titration measuring.The poly(lactic acid) of plasticizer is dissolved in the mixed solution of Ortho Cresol and chloroform, and (weight ratio is: 3/7), add bromthymol blue indicator, the ethanolic soln with the potassium hydroxide of 0.05N carries out titration then.
2. lactide monomer Determination on content in the film:
Adopt gas-chromatography (GC-14B) to measure: measuring method is the internal standard method.Condition determination:
Vaporizer temperature: 180 ℃
Analyzer temperature: 220 ℃
The intensification condition: 80 ℃ of starting temperatures, heat-up rate are 10 ℃/min, and outlet temperature is that 200 ℃ of hold-times are 5 minutes.
Injection rate: 1ul detection limit: 100ppm
3. the mensuration of molecular weight:
Measure with gel chromatography (GPC), as solvent, the poly(lactic acid) of plasticizer be made into 1mg/ml with THF, with THF as moving phase.
4.PLA the mensuration of film stretching modulus:
It is 10mm that the film of estimating usefulness is made width, and length is the sheet of 150mm, is that the damping of carrying out 1 day under 23 ℃ of humidity condition that is 65%RH is handled in temperature.This test portion is ready to according to the standard conditions of JIS K7161 and JIS K71727 under 23 ℃ condition of nitrogen gas, adopt universal testing machine UTC-100, with long 50mm of initial stage, draw speed is that the condition of 300mm per minute is carried out tension test, measures its tensile modulus.Under same level, measure 5 times during mensuration, obtain 5 times mean value with it as tensile modulus.
Claims (4)
1. the polylactic acid base polymer of a plasticizer is characterized in that: be with ferric acetyl acetonade or iron stearate as catalyzer, utilize rac-Lactide and polyalkylene ether polymer to carry out the polymkeric substance that polymerization makes; The structure of described polyalkylene ether polymer is a line polymer, is molecular weight at 1500～15000 polypropylene glycol or polytetrahydrofuran.
2. the production method of the polylactic acid base polymer of a plasticizer is characterized in that: under the condition that catalyzer exists, reaction makes the polylactic acid base polymer of plasticizer with rac-Lactide and polyalkylene ether polymer; The structure of described polyalkylene ether polymer is a line polymer, is molecular weight at 1500～15000 polypropylene glycol or polytetrahydrofuran, and described catalyzer is ferric acetyl acetonade or iron stearate.
3. the production method of the polylactic acid base polymer of plasticizer according to claim 2, it is characterized in that: the consumption of polyalkylene ether polymer is to be equivalent to 20%～80% of plasticizer polylactic acid polymer weight.
4. according to the production method of the polylactic acid base polymer of claim 2 or 3 described plasticizers, it is characterized in that: catalyst consumption be equivalent to plasticizer polylactic acid base polymer weight 0.05～3.0%.
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| CN2006101614453A CN101200533B (en) | 2006-12-12 | 2006-12-12 | Polylactide polymers for plasticizer and production method |
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| CN2006101614453A CN101200533B (en) | 2006-12-12 | 2006-12-12 | Polylactide polymers for plasticizer and production method |
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| CN101200533A CN101200533A (en) | 2008-06-18 |
| CN101200533B true CN101200533B (en) | 2011-11-02 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101875729B (en) * | 2009-04-30 | 2012-07-25 | 长春石油化学股份有限公司 | Plasticizer composition used for polyvinyl butyral and polyvinyl butyral composition |
| CN103421034B (en) * | 2013-08-09 | 2015-10-21 | 中国科学院长春应用化学研究所 | The preparation method of Chiral aluminum compound and preparation method thereof and poly(lactic acid) |
| CN103951950B (en) * | 2014-05-04 | 2016-04-13 | 电子科技大学 | Flexible biological degradable composite material |
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2006
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Non-Patent Citations (2)
| Title |
|---|
| 王小莺等.乙酰丙酮铁催化丙交酯开环聚合的研究.《高分子学报》.2005,(第1期), * |
| 葛建华等.PLA—PEG—PLA 嵌段共聚物的合成及研究.《材料科学与工程学报》.2003,第21卷(第6期), * |
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