CN101328307A - Polylactic acid plasticize product and production method - Google Patents
Polylactic acid plasticize product and production method Download PDFInfo
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- CN101328307A CN101328307A CNA2007100238522A CN200710023852A CN101328307A CN 101328307 A CN101328307 A CN 101328307A CN A2007100238522 A CNA2007100238522 A CN A2007100238522A CN 200710023852 A CN200710023852 A CN 200710023852A CN 101328307 A CN101328307 A CN 101328307A
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Abstract
The invention discloses a polylactic acid plasticized product and a preparation method thereof. Under the condition of existence of a catalyst, the ring-opening of lactides and the PBS generate a PLA-PBS-PLA copolymer via the copolymerization, and then the copolymer and the PLA are mixed to prepare the polylactic acid plasticized product. The tensile modulus of the polylactic acid film product, at the temperature of 23 DEG C, reaches 0.1 to 2 GPa; and the transmission of vapor, at the temperature of 2 DEG C, is between 15 and 25g/m<2>*24h. The transmission of vapor of the polylactic acid plasticized product is low.
Description
Technical field:
The present invention relates to polylactic acid base polymer composition, relate to plasticizer in more detail and give the low water vapor transmission rate (WVTR) that polymkeric substance flexibility, toughness and softening agent are given product.
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 still 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 to add molecular weight regulator in this process, and the purity requirement to rac-Lactide is higher, particularly the suitable complexity of the processing of moisture.
At present the multipolymer of also useful PEG and PLA is as the softening agent of PLA product, but the water vapor transmission rate (WVTR) of this product makes the purposes of product be subjected to certain restriction, requires at some that product can't be widely used aspect the low packing of water vapor transmission rate (WVTR).
PLA is the polymkeric substance of totally biodegradable, but because the adding of softening agent and conditioning agent makes that product no longer is a totally biodegradable.Therefore softening agent and the additive requirement to poly(lactic acid) is the attention that also more and more is subjected to the researchist of fully biodegradable.The many biodegradable materials of research comprise polyhydroxyalkanoate (PHA) at present, poly(lactic acid) (PLA) and poly butylene succinate (PBS), have complementary advantages if these three kinds of biodegradable materials can be carried out combination, what the application prospect of that product will be very is wide.
Summary of the invention:
The object of the present invention is to provide low polylactic acid plasticize product of a kind of water vapor transmission rate (WVTR) and production method thereof.
The technical solution that the present invention adopts is:
A kind of polylactic acid plasticize product is characterized in that: being to use the PLA-PBS-PLA multipolymer that formed by PLA and PBS copolymerization and PLA to carry out blend to make, is 12 μ m at thickness, and water vapor transmission rate (WVTR) is 15～25g/m under the condition when probe temperature is 2 ℃
2* 24h.
A kind of production method of polylactic acid plasticize product is characterized in that: utilize rac-Lactide open loop and PBS to carry out copolymerization under the situation that catalyzer exists and form the PLA-PBS-PLA multipolymer, utilize this multipolymer and PLA to carry out blend again, make polylactic acid plasticize product.
The catalyzer that rac-Lactide open loop and PBS carry out copolyreaction is that ferric acetyl acetonade or stearic acid are ferrous.
Above-mentioned catalyst consumption is to be equivalent to 0.05～1.0% of PLA-PBS-PLA multipolymer weight.
The weight percentage that the PBS consumption accounts for the PLA-PBS-PLA multipolymer is 20%～80%.
The weight percentage that the consumption of PLA-PBS PLA multipolymer accounts for polylactic acid plasticize product is 10%～80%.
The number-average molecular weight of PLA-PBS-PLA multipolymer is 7500～16000, and molecular weight distribution mw/mn is 1.1～1.5; Wherein the number-average molecular weight of PBS is 4000～8000.
Compare with technology in the past, beneficial effect of the present invention is: tensile modulus can reach 0.1～2GPa when product film of the present invention was 23 ℃ in temperature.The content of oligopolymer is below 2wt% in the final film; The water vapor transmission rate (WVTR) of this product is simultaneously: 15～25g/m2*24h (condition determination: thickness of sample 12 μ m, measuring temperature is 2 ℃), make that product has obtained in the lower field of water vapor transmission rate (WVTR) requirement using widely; The poly(lactic acid) of the plasticizer that the present invention makes is the segmented copolymer of PLA and PBS, therefore the consistency of this plasticizer and PLA is better, in use 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; Because the catalyzer that uses is the compound of iron, not only price comparison cheaply and also the metallization of in use separating out and thing can not make poison, make the restriction aspect the health that is subjected to of use range of product like this; The main component of this product is exactly PLA and two kinds of polymkeric substance of PBS, and these two kinds of polymkeric substance are again totally biodegradables, so this plasticity poly-lactic acid products also is fully biodegradable, and discontinued product can recycling be the compost of plant-growth.
The preparation of PBS:
Tell adding 59 gram Succinic Acid (Chemical Reagent Co., Ltd., Sinopharm Group) and 54 gram butyleneglycols (G three-dimensional) in the mouth test tube in clean having, load onto then and overlap in the silicone oil groove that head is put into 210 ℃, connect and stir, the speed of stirring is transferred to 30rpm, and logical rapidly nitrogen carries out protective reaction 3h; Slowly vacuumize then and make resulting pressure about 200Pa, and carry out vacuum reaction 3h.At last product is spued, and logical nitrogen is protected and is cooled to room temperature until product and promptly obtains the thick product of PBS.The thick product of PBS is dissolved in the chloroform (Shen, Shanghai credit chemical company limited) of 400ml and and carries out reprecipitation with a large amount of cold methanol (Shanghai chemical reagent company limited); repeat such reprecipitation 2～3 times, at last the PBS product is at room temperature carried out drying until constant weight.
The PBS that makes like this through its number-average molecular weight of GPC determining molecular weight is: 4000～8000, and its molecular weight distribution mw/mn is: 1.1～1.5; COOH content is: 3～8eq/t; Can learn that from the content of COOH the end group of PBS is OH, for the triblock copolymer for preparing PLA-PBS-PLA provides possibility.
The plasticity poly-lactic acid products is a fully biodegradable, and in use plasticizer can not move from poly-lactic acid products, makes increase greatly the work-ing life of product; Catalyzer can in use not separated out intoxicating as heavy metal catalyst in the past yet, thereby the use range of product becomes more extensive; The Young's modulus of this product is with suitable as the poly-lactic acid products of softening agent with PLA-PEG-PLA, but the water vapor transmission rate (WVTR) of this product is lower much than it, has developed ideal product for requiring the low film packaging industry of water vapor transmission rate (WVTR); Because two big major ingredient (PLA, PBS) of product are the polymkeric substance of totally biodegradable, so the product that obtains is a totally biodegradable, for in the treating processes generation of product after using, come convenience, do not need to spend a large amount of expenses and carry out waste treatment, but can be recycled as the compost of plant-growth.
Embodiment 1:
The PBS 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 PBS 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 (Dutch purac company), 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 (Shanghai San'aisi Reagent Co., Ltd.) (0.1mol/ml, 2.5ml), toluene (Jiangsu Jin Cheng chemical reagent work) is solvent), feeding nitrogen reacted 2 hours down after continuing displacement 3 bouts, add deactivator phosphoric acid crystallisate (SIGMA-ALDRICH) (0.1mol/ml again, 0.09ml) feed nitrogen down reaction begin devolatilization after 20 minutes, slowly vacuumize half an hour, resulting pressure is about 200Pa, spues at last, obtains the PLA-PBS-PLA multipolymer.
The preparation of the polylactic acid-based product of plasticity:
Taking by weighing PLA-PBS-PLA multipolymer 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 PBS consumption is 20g, and the consumption of rac-Lactide is 80g.
Embodiment 3:
Experimentation and condition are identical with embodiment 1, and the PBS consumption is 40g, and the consumption of rac-Lactide is 60g.
Embodiment 4:
Experimentation and condition are identical with embodiment 1, and the PBS consumption is 80g, and the rac-Lactide consumption is 20g.
Embodiment 5
Experimentation and condition are identical with embodiment 1, and the consumption of PLA-PBS-PLA is 50g, and the consumption of poly(lactic acid) is 50g.
Embodiment 6:
Experimentation and condition are identical with embodiment 1, and the consumption of PLA-PBS-PLA is 70g, and the consumption of poly(lactic acid) is 30g.
Embodiment 7:
Experimentation and condition are identical with embodiment 1, and catalyst consumption is 0.1mol/L, and 1.5ml, toluene are solvent.
Embodiment 8:
Experimentation and condition are identical with embodiment 1, and catalyst consumption is 0.1mol/L, and 5ml, toluene are solvent.
Embodiment 9:
Experimentation is identical with embodiment 1 with condition, and the amount of catalyzer is 0.1mol/L, 10ml, and toluene is as flux.
Embodiment 10:
Experimentation is identical with embodiment 1 with condition, catalyzer be iron stearate (stremchemical, consumption are 0.1mol/L, 2.5ml, toluene is as flux.
Comparative example 1:
Experimentation is identical with embodiment 1 with condition, and PBS uses instead into PEG-6000 (pharmaceutical excipient factory of Liaoyang Huaxing), and consumption is 58.9g.The technical indicator of product:
From top form as can be seen: 1. the technical target of the product that makes as catalyzer with ferric acetyl acetonade can reach fully in the past with the product of tin compound as catalyzer.Ferrous this catalyst for reaction that can be used as fully of ferric acetyl acetonade and stearic acid reduces the price of catalyzer greatly, and in use also can not produce separating out of toxic heavy metal.Use the compound of iron 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; 2. suitable as the technical indicator of the product that makes of plasticizer and technical indicator that PEG makes with PBS, and low the manying of product that the transmitance of water vapour makes as plasticizer than PEG make PBS have own special advantages like this, make that the purposes of product is clearer and more definite; 3.PBS the green material and the PLA fully biodegradable that are totally biodegradable are complementary, and make that final film product also is a totally biodegradable, the direction of the current investigation of materials of PDT R﹠D Representative of this material.
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:
(GC-14B, SHIMADZU) measure: measuring method is the internal standard method to adopt gas-chromatography.
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, SHIMADZU LC-10A), 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, adopts universal testing machine UTC-100, and 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.
5. the mensuration of water vapor transmission rate (WVTR):
At internal diameter is the water that adds about 20g in the aluminum container of 60mm, uses the mouth of ready film sample title container then, and weigh.It is 2 ℃ that temperature is set, and humidity is 90% thermostatic equipment, places its weight of weighing after 3 days in equipment.Calculate its Water Vapour Permeability then.
Water vapor transmission rate (WVTR) is=weight front and back variable quantity (g)/vessel port area (m
2) * 72 hours.
Claims (7)
1, a kind of polylactic acid plasticize product is characterized in that: being to use the PLA-PBS-PLA multipolymer that formed by PLA and PBS copolymerization and PLA to carry out blend to make, is 12 μ m at thickness, and water vapor transmission rate (WVTR) is 15～25g/m under the condition when probe temperature is 2 ℃
2* 24h.
2, a kind of production method of polylactic acid plasticize product is characterized in that: utilize rac-Lactide open loop and PBS to carry out copolymerization under the situation that catalyzer exists and form the PLA-PBS-PLA multipolymer, utilize this multipolymer and PLA to carry out blend again, make polylactic acid plasticize product.
3, the production method of polylactic acid plasticize product according to claim 2 is characterized in that: the catalyzer that rac-Lactide open loop and PBS carry out copolyreaction is that ferric acetyl acetonade or stearic acid are ferrous.
4, the production method of polylactic acid plasticize product according to claim 3 is characterized in that: above-mentioned catalyst consumption is to be equivalent to 0.05～1.0% of PLA-PBS-PLA multipolymer weight.
5, according to the production method of claim 2,3 or 4 described polylactic acid plasticize products, it is characterized in that: the weight percentage that the PBS consumption accounts for the PLA-PBS-PLA multipolymer is 20%～80%.
6, according to the production method of claim 2,3 or 4 described polylactic acid plasticize products, it is characterized in that: the weight percentage that the consumption of PLA-PBS-PLA multipolymer accounts for polylactic acid plasticize product is 10%～80%.
7, according to the production method of claim 2,3 or 4 described polylactic acid plasticize products, it is characterized in that: the number-average molecular weight of PLA-PBS-PLA multipolymer is 7500～16000, and molecular weight distribution mw/mn is 1.1～1.5; Wherein the number-average molecular weight of PBS is 4000～8000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100238522A CN101328307A (en) | 2007-06-22 | 2007-06-22 | Polylactic acid plasticize product and production method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100238522A CN101328307A (en) | 2007-06-22 | 2007-06-22 | Polylactic acid plasticize product and production method |
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| CN101328307A true CN101328307A (en) | 2008-12-24 |
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| CNA2007100238522A Pending CN101328307A (en) | 2007-06-22 | 2007-06-22 | Polylactic acid plasticize product and production method |
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2007
- 2007-06-22 CN CNA2007100238522A patent/CN101328307A/en active Pending
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Open date: 20081224 |