CN101302281A - Polylactic acid and preparation thereof - Google Patents
Polylactic acid and preparation thereof Download PDFInfo
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- CN101302281A CN101302281A CNA2007100222399A CN200710022239A CN101302281A CN 101302281 A CN101302281 A CN 101302281A CN A2007100222399 A CNA2007100222399 A CN A2007100222399A CN 200710022239 A CN200710022239 A CN 200710022239A CN 101302281 A CN101302281 A CN 101302281A
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Abstract
The invention discloses a poly lactic acid containing a rare earth compound(C1) or a rare earth compound(C1) and a sulfonic acid compound(C2). The weight mean molecular weight of the poly lactic acid is between 5,000 and 50,000, and at a temperature of 180 DEG C and in a nitriding atmosphere, the thermal degradation speed is less than 0.87 weight percent/min. The invention also discloses a method for preparing the poly lactic acid, wherein the method comprises the following steps that: an L-lactic acid, a D-lactic acid and a mixture of the L-lactic acid and the D-lactic acid or a low polymer of the L-lactic acid and the D-lactic acid are taken as materials, and the materials are added with the rare earth compound(C1) or added with the rare earth compound(C1) and the sulfonic acid compound(C2) at the same time for the melt polycondensation reaction, and the poly lactic acid is obtained. The poly lactic acid obtained by the method has the thermal stability far better than that of the sample prepared by the tin catalyst under the same condition and the thermal degradation speed lowered by one order of magnitude compared with the sample prepared by the tin catalyst under the same condition.
Description
Technical field
The present invention relates to the organic polymer field, relate to a kind of poly(lactic acid) that contains rare earth compound and preparation method thereof specifically.
Background technology
Poly(lactic acid) (PLA) has excellent biological compatibility and biological degradability, and degraded product can participate in the metabolism of human body, with and performance can be by adjusted on a large scale with other monomer copolymerizations, current one of the most valued biodegradation type material that become.
PLA can be by open loop (indirectly) method and directly condensation method preparation.The open loop method is earlier acid by dehydrating lactic to be made its lactide dimer, and then ring-opening polymerization obtains poly(lactic acid) to rac-Lactide.It is higher that this method obtains the PLA molecular weight, and thermostability is also better, but indirect method requires highly purified rac-Lactide, and complex manufacturing, causes the price height of poly(lactic acid), is difficult to and the general-purpose plastics competition, thereby limited its widespread use.Owing to lactic acid is to be come by reproducible farm crop fermentation, make direct condensation method become and prepare the simple economic again method of poly(lactic acid) to have very big prospects for commercial application, receive increasing concern in recent years.
At present, many patent or documents that relate to the poly(lactic acid) preparation method are arranged, except that Nature Works is equipped with the high molecular weight polylactic acid by the open loop legal system with traditional stannous octoate, the Mitsui of Japan discloses in US6140458 and has adopted glass putty, tin protoxide and volatile organic sulfonic acid single component as the catalyzer of lactic acid direct condensation, can obtain weight-average molecular weight and reach 300,000 poly(lactic acid) behind solid phase polycondensation; The Kimura of capital of a country Polytechnics finds with tin protochloride/tosic acid binary catalyst the lactic acid direct condensation to be had good catalytic effect, and they carry out solid state polymerization with oligopolymer below fusing point, can obtain weight-average molecular weight up to 500,000 poly(lactic acid).Tradition tin class catalyzer has advantages of high catalytic activity to monomer polymerization, and its degraded to poly(lactic acid) simultaneously also has good catalytic effect.Thereby traditional tin class catalyzer is difficult to the poly(lactic acid) that makes optical purity or have high thermal stability.Volatile sulfonic acid is because its volatility causes polymerization efficiency low, and the reaction times is very long.Therefore, effective, the cheap catalyzer of development of new is the key of research lactic acid polycondensation.
In recent years, rare earth compound as catalyzer since its high reactivity and hypotoxicity be subjected to Chinese scholars and paid close attention to widely, utilize rare earth compound to prepare existing the delivering of relevant patent of biodegradation type polyester, disclose with the trifluoromethanesulfonic acid rare earth as Japanese patent application JP2003-306535A and to have made catalyst aliphatic diol and diacid reactant, prepared corresponding aliphatic polyester; Be catalyzer with samarium and the rare earth compound heavier than samarium among the JP6-329777, direct method obtains aromatic polyester; Disclose respectively with the catalysis of rare-earth compound cyclic esters ring-opening polymerization among JP7-502772 and the JP2003-313282A and prepared aliphatic polyester.China is rare earth big country, and proven reserve account for global about 80%.In many Chinese patent application, CN1146466A discloses with alkyl rare earth compound and allyl group rare earth compounding, causes cyclic esters ring-opening polymerizations such as caprolactone, rac-Lactide and obtains biodegradable aliphatic polyester; It is catalyzer that CN14446837A discloses with lanthanide series metal halogeno salt and/or lanthanide metal-complexed thing and lanthanide series metal oxyhydroxide mixture, can make in the synthesizing polyester process transesterification reaction quick, carries out stably; Disclose rare earth compound and titanium sub-group compound rare earth compound compound or single component among the CN1796434A and prepared the aromatic-aliphatic polyester, can obtain the product that molecular weight is higher, color is more shallow in the shorter reaction times than traditional Titanium series catalyst.
Tin class catalyzer is used in the polycondensation of present lactic acid mostly.Owing to contain a small amount of tin metal in the synthetic poly(lactic acid), make the thermal destruction speed height of poly(lactic acid), poor heat stability brings serious problems for follow-up processed and applied.And if a small amount of tin metal of removing in the poly(lactic acid) to be contained, process more complicated and cost are than higher.
As mentioned above, rare earth compound prepares existing performance preferably aspect the polyester in the open loop method or by diacid and glycol, but prepare the poly(lactic acid) field in direct method, still there be not delivering of rare earth compound research application, therefore be necessary to provide a kind of use novel rare-earth compound system, existing poly(lactic acid) synthesis technique can be simplified, the method for poly(lactic acid) can be prepared again with excellent heat stability.
Summary of the invention
The objective of the invention is in order to overcome the deficiency that existing catalyzer exists in the lactic acid polycondensation field, for example avoid in the poly(lactic acid) because of existing tin metal to bring variety of issue, and the application of further expanding rare earth compound, what a kind of single component rare earth compound that contains nontoxic or low toxicity or rare earth compound and volatile sulfonic acid composite catalyst were provided does not contain tin metal, can improve the poly(lactic acid) of thermostability simultaneously again.
Another object of the present invention provides a kind of preparation method of above-mentioned poly(lactic acid).
Purpose of the present invention can reach by following measure:
A kind of poly(lactic acid), described poly(lactic acid) contains rare earth compound C1, perhaps also contains sulfoacid compound C2; The weight-average molecular weight of poly(lactic acid) is 5,000～50,000, and its thermal destruction speed in 180 ℃ nitrogen atmosphere is lower than 0.87wt%/min.
Rare earth compound C1 is selected from rare earth oxide Ln
2O
3, rare earth halide LnX
3, rare earth sulfonate Ln (R1SO
3)
3Or Ln (Ar1SO
3)
3, RE phosphate Ln (P204)
3Or Ln (P507)
3, rare earth carboxylate Ln (R2COO)
3Or Ln (Ar2COO)
3Or rare earth naphthenate Ln (naph)
3In one or more; Wherein, X is a haloid element, and R1 is the C that halogen replaces or do not have replacement
1～C
3Alkyl, Ar1 is phenyl or C
1～C
3The phenyl that replaces of alkyl, naph is the cycloalkanes acidic group, P204 is a di (isooctyl) phosphate, P507 is the different monooctyl ester of mono phosphoric acid ester; R2 is the alkyl of C1～C11, and Ar2 is a phenyl; Ln is a rare earth metal, is selected from the periodic table of elements in the IIIB family in 15 lanthanon or scandium or the yttrium one or more.
Rare earth compound C1 is preferably selected from rare earth oxide Ln
2O
3, rare earth halide LnX
3, rare earth sulfonate Ln (R1SO
3)
3Or Ln (Ar1SO
3)
3Or rare earth carboxylate Ln (R2COO)
3Or Ln (Ar2COO)
3In a kind of; Wherein X is a chlorion, and R1 is a trifluoromethyl, Ar1 be dodecane for phenyl, R2 is undecyl or 2-ethyl pentyl group, Ar2 is a phenyl, Ln is a rare earth metal, is selected from the periodic table of elements in the IIIB family in 15 lanthanon or scandium or the yttrium one or more.
Above-mentioned rare earth metal Ln is preferably lanthanum La, praseodymium Pr, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er or yttrium Y, most preferably is lanthanum La, neodymium Nd, samarium Sm, europium Eu or erbium Er.
Sulfoacid compound C2 is aliphatic sulfonic R3SO
3H or aromatic sulphonic acid Ar3SO
3H; Wherein R3 is the C that halogen replaces or do not have replacement
1～C
3Alkyl, Ar3 for do not have to replace, C
1～C
3The phenyl that alkyl replaces or halogen replaces.
Sulfoacid compound C2 is preferably selected from methylsulfonic acid (CH
3SO
3H), ethyl sulfonic acid (C
2H
5SO
3H), 1-propyl sulfonic acid (1-C
3H
7SO
3H), Phenylsulfonic acid (C
6H
5SO
3H), tosic acid (p-CH
3C
6H
5SO
3H), p-chlorobenzenesulfonic acid (p-ClC
6H
5SO
3H) with trifluoromethanesulfonic acid (CF
3SO
3H) one or more in.
Rare earth compound C1 is 200～70000ppm of poly(lactic acid) quality, preferred 1000～20000ppm; Sulfoacid compound C2 is 0～50000ppm of poly(lactic acid) quality, preferred 1000～10000ppm.
A kind of method for preparing the described poly(lactic acid) of claim 1, mixture or their oligopolymer with L-lactic acid, D-lactic acid, L-lactic acid and D-lactic acid are raw material, add rare earth compound C1 or add rare earth compound C1 simultaneously and sulfoacid compound C2 as catalyzer, carry out melt polycondensation reaction, promptly obtain the poly(lactic acid) product.
In melt polycondensation reaction, condensation temp is 100 ℃～200 ℃, preferred 120 ℃～180 ℃; Its condensation pressure is along with the process of reaction reduces gradually, and original pressure is a normal atmosphere, and resulting pressure is 0.1KPa～6KPa, perhaps directly reacts under the pressure of 0.1KPa～6Kpa; The condensation time is 3h～20h, preferred 6～15h.
Reaction is carried out under decompression or vacuum usually, also can carry out in rare gas element (as nitrogen).
In a preferred embodiment of the invention, catalyzer of the present invention comprises:
C1 is selected from the rare earth oxide Ln of rare earth compound
2O
3, rare earth chloride LnX
3, rare earth sulfonate Ln (R1SO
3)
3Or Ln (Ar1SO
3)
3With rare earth carboxylate Ln (R2COO)
3Or Ln (Ar2COO)
3In a kind of,
And C2, be selected from methylsulfonic acid (CH
3SO
3H), ethyl sulfonic acid (C
2H
5SO
3H), 1-propyl sulfonic acid (1-C
3H
7SO
3H), Phenylsulfonic acid (C
6H
5SO
3H), tosic acid (p-CH
3C
6H
5SO
3H), p-chlorobenzenesulfonic acid (p-ClC
6H
5SO
3H) with trifluoromethanesulfonic acid (CF
3SO
3H) at least a in.
And the mol ratio of described C1 and C2 is 100: 0～1: 100.
Wherein, described rare earth metal Ln is selected from a kind of among lanthanum La, neodymium Nd, samarium Sm, europium Eu, the erbium Er; X is a chlorion; Ar1 is that dodecane is for phenyl; R2 is undecyl or 2-ethyl pentyl group; Ar2 is a phenyl.
The catalyst system that is used for the lactic acid polycondensation of the present invention can single component C1 or C1 and C2 multicomponent mixture mixed system.
Beneficial effect of the present invention is as follows:
The 1 rare earth compound C1 that contains of the present invention, the poly(lactic acid) that perhaps also contains sulfoacid compound C2 has superior thermostability;
2 catalyzer of the present invention have and the approaching catalytic activity of tin class catalyzer, and the polylactic acid molecule amount narrowly distributing that obtains;
3 poly(lactic acid) of the present invention are pure, do not contain additives such as expanding connection agent, stablizer;
4 catalyzer of the present invention are low to the catalytic activity of poly(lactic acid) degraded, compare with tin class catalyzer, and thermal stability is significantly increased, and its thermal destruction speed ratio latter hangs down an order of magnitude.
Embodiment
In following examples and the comparative example, polymericular weight records on ShimadzuLC-20AD with gel chromatography, and solvent for use is a tetrahydrofuran (THF), and standard is a polystyrene; The thermal destruction speed of polymkeric substance (thermal weight loss speed) uses TA Q100 to record in 180 ℃ nitrogen atmosphere.
Embodiment 1:
Be equipped with to 250ml that to add 110g purity in the three-necked bottle of agitator and prolong be 90% L-lactic acid and lanthanum trioxide 0.2g, vacuumize and replace nitrogen 3-5 time.System put into 120 ℃ oil bath, be to stir dehydration 1h under the condition of 40KPa at pressure, in 0.5 hour, pressure is progressively dropped to 1KPa then, simultaneous temperature rises to 180 ℃, continue to stir 7 hours, the weight-average molecular weight that obtains is 30,000, molecular weight distribution is 1.57 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.11wt%/min.
Embodiment 2:
Be equipped with to 250ml that to add 110g purity in the three-necked bottle of agitator and prolong be 90% L-lactic acid and Neodymium trioxide 0.21g, vacuumize and replace nitrogen 3-5 time.System put into 120 ℃ oil bath, be to stir dehydration 1h under the condition of 40KPa at pressure, in 0.5 hour, pressure is progressively dropped to 1KPa then, simultaneous temperature rises to 180 ℃, continue to stir 7 hours, the weight-average molecular weight that obtains is 20,000, molecular weight distribution is 1.59 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.12wt%/min.
Embodiment 3:
Be equipped with to 250ml that to add 110g purity in the three-necked bottle of agitator and prolong be 90% D-lactic acid and Samarium trioxide 0.23g, vacuumize and replace nitrogen 3-5 time.System put into 100 ℃ oil bath, be to stir dehydration 1h under the condition of 40KPa at pressure, in 0.5 hour, pressure is progressively dropped to 1KPa then, simultaneous temperature rises to 180 ℃, continue to stir 7 hours, the weight-average molecular weight that obtains is 31,000, molecular weight distribution is 1.67 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.12wt%/min.
Embodiment 4:
Be equipped with to 250ml that to add 110g purity in the three-necked bottle of agitator and prolong be 90% D-lactic acid and europium sesquioxide 0.24g, vacuumize and replace nitrogen 3-5 time.System put into 100 ℃ oil bath, be to stir dehydration 1h under the condition of 40KPa at pressure, in 0.5 hour, pressure is progressively dropped to 1KPa then, simultaneous temperature rises to 180 ℃, continue to stir 7 hours, the weight-average molecular weight that obtains is 28,000, molecular weight distribution is 1.61 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.1wt%/min.
Embodiment 5:
Be equipped with to 250ml and add 100g D-acid by dehydrating lactic oligopolymer (Mw=2000) and Lanthanum trichloride 0.33g in the three-necked bottle of agitator and prolong, vacuumize and replace nitrogen 3-5 time.System is put into 190 ℃ oil bath, is stirring reaction 7h under the condition of 1KPa at pressure, and the weight-average molecular weight that obtains is 40,000, molecular weight distribution is 1.66 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.086wt%/min.
Embodiment 6:
Be equipped with to 250ml and add 100g L-acid by dehydrating lactic oligopolymer (Mw=5000) and Lanthanum trichloride 0.33g in the three-necked bottle of agitator and prolong, vacuumize and replace nitrogen 3-5 time.System is put into 140 ℃ oil bath, is stirring reaction 7h under the condition of 5.5KPa at pressure, and the weight-average molecular weight that obtains is 32,000, molecular weight distribution is 1.56 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.1wt%/min.
Embodiment 7:
In the eggplant-shape bottle of 250ml, add 100g L-acid by dehydrating lactic oligopolymer (Mw=1500) and samarium trichloride 0.34g, vacuumize and replace nitrogen 3-5 time.System put into 160 ℃ oil bath, be on Rotary Evaporators, to react under the condition of 5.5KPa at pressure, rotating speed is 50r/min, the weight-average molecular weight that obtains behind the 10h is 26,000, molecular weight distribution is 1.56 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.14wt%/min.
Embodiment 8:
Be equipped with to 250ml and add 110g L-lactic acid and Neodymium trichloride 1.02g in the three-necked bottle of agitator and prolong, vacuumize and replace nitrogen 3-5 time.System is put into 180 ℃ oil bath, is stirring reaction 12h under the condition of 3KPa at pressure, and the weight-average molecular weight that obtains is 50,000, molecular weight distribution is 1.65 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.41wt%/min.
Embodiment 9:
Be equipped with to 250ml and add 110g L-lactic acid and Europium trichloride 0.35g in the three-necked bottle of agitator and prolong, vacuumize and replace nitrogen 3-5 time.System is put into 180 ℃ oil bath, is stirring reaction 15h under the condition of 0.4KPa at pressure, and the weight-average molecular weight that obtains is 48,000, molecular weight distribution is 1.65 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.16wt%/min.
Embodiment 10:
In the eggplant-shape bottle of 250ml, add 100g L-acid by dehydrating lactic oligopolymer (Mw=2000) and trifluoromethanesulfonic acid neodymium 1.58g, vacuumize and replace nitrogen 3-5 time.System put into 200 ℃ oil bath, be on Rotary Evaporators, to react under the condition of 0.8KPa at pressure, rotating speed is 50r/min, the weight-average molecular weight that obtains behind the 12h is 31,000, molecular weight distribution is 1.73 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.05wt%/min.
Embodiment 11:
In the eggplant-shape bottle of 250ml, add 110g L-lactic acid and lauric acid neodymium 0.96g, vacuumize and replace nitrogen 3-5 time.System put into 160 ℃ oil bath, be on Rotary Evaporators, to react under the condition of 0.5KPa at pressure, rotating speed is 50r/min, the weight-average molecular weight that obtains behind the 20h is 49,000, molecular weight distribution is 1.63 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.06wt%/min.
Embodiment 12:
In the eggplant-shape bottle of 250ml, add 110g L-lactic acid and phenylformic acid europium 0.85g, vacuumize and replace nitrogen 3-5 time.System put into 160 ℃ oil bath, be on Rotary Evaporators, to react under the condition of 0.5KPa at pressure, rotating speed is 50r/min, the weight-average molecular weight that obtains behind the 15h is 46,000, molecular weight distribution is 1.66 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.03wt%/min.
Embodiment 13:
Be equipped with to 250ml and add 100g L-acid by dehydrating lactic oligopolymer (Mw=2000) and methylsulfonic acid samarium 0.58g in the three-necked bottle of agitator and prolong, vacuumize and replace nitrogen 3-5 time.System is put into 160 ℃ oil bath, is stirring reaction 7h under the condition of 0.3KPa at pressure, and the weight-average molecular weight that obtains is 16,900, molecular weight distribution is 1.49 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.07wt%/min.
Embodiment 14:
In the eggplant-shape bottle of 250ml, add 110g L-lactic acid and lanthanum (P507) 1.34g, vacuumize and replace nitrogen 3-5 time.System put into 180 ℃ oil bath, be to react on Rotary Evaporators under the condition of 0.3KPa at pressure, rotating speed is 50r/min, and the weight-average molecular weight that obtains behind the 7h is 13,400, molecular weight distribution is 1.58 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.16wt%/min.
Embodiment 15:
In the eggplant-shape bottle of 250ml, add 100g L-acid by dehydrating lactic oligopolymer (Mw=2000) and tosic acid neodymium 0.87g, vacuumize and replace nitrogen 3-5 time.System put into 160 ℃ oil bath, be to react on Rotary Evaporators under the condition of 1KPa at pressure, rotating speed is 50r/min, and the weight-average molecular weight that obtains behind the 10h is 24,200, molecular weight distribution is 1.69 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.08wt%/min.
Embodiment 16:
In the eggplant-shape bottle of 250ml, add 100g L-acid by dehydrating lactic oligopolymer (Mw=2000) and protactinium oxide 0.23g, vacuumize and replace nitrogen 3-5 time.System put into 200 ℃ oil bath, be to react on Rotary Evaporators under the condition of 0.2KPa at pressure, rotating speed is 50r/min, and the weight-average molecular weight that obtains behind the 3h is 17,200, molecular weight distribution is 1.57 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.17wt%/min.
Embodiment 17:
In the eggplant-shape bottle of 250ml, add 100g L-acid by dehydrating lactic oligopolymer (Mw=2000) and Neodymium trichloride 0.05g, vacuumize and replace nitrogen 3-5 time.System put into 100 ℃ oil bath, be to react on Rotary Evaporators under the condition of 3KPa at pressure, rotating speed is 50r/min, and the weight-average molecular weight that obtains behind the 7h is 5,000, molecular weight distribution is 1.66 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.11wt%/min.
Embodiment 18:
In the eggplant-shape bottle of 250ml, add 100g L-acid by dehydrating lactic oligopolymer (Mw=2000) and Dysprosium trichloride 0.36g, vacuumize and replace nitrogen 3-5 time.System put into 130 ℃ oil bath, be to react on Rotary Evaporators under the condition of 0.8KPa at pressure, rotating speed is 50r/min, and the weight-average molecular weight that obtains behind the 7h is 12,700, molecular weight distribution is 1.65 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.13wt%/min.
Embodiment 19:
In the eggplant-shape bottle of 250ml, add 100g L-acid by dehydrating lactic oligopolymer (Mw=2000) and Samarium trioxide 0.22g and tosic acid 0.48g, vacuumize and replace nitrogen 3-5 time.System put into 160 ℃ oil bath, be to react on Rotary Evaporators under the condition of 1KPa at pressure, rotating speed is 50r/min, and the weight-average molecular weight that obtains behind the 7h is 19,600, molecular weight distribution is 1.56 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.09wt%/min.
Embodiment 20:
In the eggplant-shape bottle of 250ml, add 100g L-acid by dehydrating lactic oligopolymer (Mw=2000) and Lanthanum trichloride 0.33g and methylsulfonic acid 0.192g, vacuumize and replace nitrogen 3-5 time.System is put into 160 ℃ oil bath, is to react on Rotary Evaporators under the condition of 0.8KPa at pressure, and rotating speed is 50r/min, and the weight-average molecular weight that obtains behind the 7h is 25,600, molecular weight distribution is 1.66 poly(lactic acid).
Embodiment 21:
In the eggplant-shape bottle of 250ml, add 100g L-acid by dehydrating lactic oligopolymer (Mw=2000) and Lanthanum trichloride 0.33g and methylsulfonic acid 0.096g, vacuumize and replace nitrogen 3-5 time.System put into 160 ℃ oil bath, be to react on Rotary Evaporators under the condition of 1KPa at pressure, rotating speed is 50r/min, and the weight-average molecular weight that obtains behind the 7h is 21,400, molecular weight distribution is 1.61 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.08wt%/min.
Embodiment 22:
In the eggplant-shape bottle of 250ml, add 100g L-acid by dehydrating lactic oligopolymer (Mw=2000) and Neodymium trichloride 0.34g and ethyl sulfonic acid 3.8g, vacuumize and replace nitrogen 3-5 time.System put into 160 ℃ oil bath, be to react on Rotary Evaporators under the condition of 1KPa at pressure, rotating speed is 50r/min, and the weight-average molecular weight that obtains behind the 7h is 31,000, molecular weight distribution is 1.67 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.09wt%/min.
Embodiment 23:
Be equipped with to 250ml and add 110g L-lactic acid and Lanthanum trichloride 0.33g and methylsulfonic acid 0.30g in the three-necked bottle of agitator and prolong, vacuumize and replace nitrogen 3-5 time.System is put into 180 ℃ oil bath, is stirring reaction 7h under the condition of 1KPa at pressure, and the weight-average molecular weight that obtains is 20,600, molecular weight distribution is 1.67 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.1wt%/min.
Embodiment 24:
In the eggplant-shape bottle of 250ml, add 100g L-acid by dehydrating lactic oligopolymer (Mw=2000) and Neodymium trichloride 0.34g and methylsulfonic acid 0.048g, vacuumize and replace nitrogen 3-5 time.System put into 160 ℃ oil bath, be to react on Rotary Evaporators under the condition of 1KPa at pressure, rotating speed is 50r/min, and the weight-average molecular weight that obtains behind the 7h is 31,000, molecular weight distribution is 1.67 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.08wt%/min.
Embodiment 25:
In the eggplant-shape bottle of 250ml, add 100g L-acid by dehydrating lactic oligopolymer (Mw=2000) and europium sesquioxide 0.05g and tosic acid 4.75g, vacuumize and replace nitrogen 3-5 time.System put into 160 ℃ oil bath, be to react on Rotary Evaporators under the condition of 1KPa at pressure, rotating speed is 50r/min, and the weight-average molecular weight that obtains behind the 7h is 31,000, molecular weight distribution is 1.67 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.11wt%/min.
Embodiment 26:
Be equipped with to 250ml and add 100g L-acid by dehydrating lactic oligopolymer (Mw=2000) and Neodymium trichloride 0.33g in the three-necked bottle of agitator and prolong, vacuumize and replace nitrogen 3-5 time.System is put into 160 ℃ oil bath, is stirring reaction 15h under the condition of 1KPa at pressure, and the weight-average molecular weight that obtains is 46,000, molecular weight distribution is 1.67 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.16wt%/min.
Embodiment 27:
In the eggplant-shape bottle of 250ml, add 100g L-acid by dehydrating lactic oligopolymer (Mw=2000) and Lanthanum trichloride 0.33g, vacuumize and replace nitrogen 3-5 time.System put into 160 ℃ oil bath, be to react on Rotary Evaporators under the condition of 1KPa at pressure, rotating speed is 50r/min, and the weight-average molecular weight that obtains behind the 12h is 45,000, molecular weight distribution is 1.70 poly(lactic acid), and its thermal destruction speed in 180 ℃ nitrogen atmosphere is 0.16wt%/min.
Comparative example 1:
Be equipped with to 250ml and add 100g L-acid by dehydrating lactic oligopolymer (Mw=2000) and tin protochloride 0.25g in the three-necked bottle of agitator and prolong, vacuumize and replace nitrogen 3-5 time.System is put into 160 ℃ oil bath, is stirring reaction 7h under the condition of 1KPa at pressure, and the weight-average molecular weight that obtains is 33,000, molecular weight distribution is 1.60 poly(lactic acid), and its thermal destruction speed is 0.87wt%/min.
Comparative example 2:
The oligopolymer that adds 100g L-lactic acid in the three-necked bottle of agitator and prolong is housed to 250ml, vacuumizes and replace nitrogen 3-5 time.System is put into 160 ℃ oil bath, is stirring reaction 7h under the condition of 1KPa at pressure, and the weight-average molecular weight that obtains is 6,000, molecular weight distribution is 1.87 poly(lactic acid).
By above embodiment as can be seen, polycondensation has advantages of high catalytic activity (comparative examples 2) to rare earth compound to lactic acid.Wherein, Samarium trioxide, europium sesquioxide, Lanthanum trichloride, Neodymium trichloride, the lauric acid neodymium is compared with being widely used in the catalytic tin protochloride of lactic acid polycondensation now rare earth compounds such as benzene methanesulfonic acids, has close catalytic activity.More prior is the thermostability that the thermostability of catalysis of rare-earth compound gained poly(lactic acid) is far superior to tin catalysis gained poly(lactic acid).
Claims (11)
1, a kind of poly(lactic acid) is characterized in that containing in the described poly(lactic acid) rare earth compound C1, perhaps also contains sulfoacid compound C2; The weight-average molecular weight of poly(lactic acid) is 5,000～50,000, and its thermal destruction speed in 180 ℃ nitrogen atmosphere is lower than 0.87wt%/min.
2, poly(lactic acid) according to claim 1 is characterized in that described rare earth compound C1 is selected from rare earth oxide Ln
2O
3, rare earth halide LnX
3, rare earth sulfonate Ln (R1SO
3)
3Or Ln (Ar1SO
3)
3, RE phosphate Ln (P204)
3Or Ln (P507)
3, rare earth carboxylate Ln (R2COO)
3Or Ln (Ar2COO)
3Or rare earth naphthenate Ln (naph)
3In one or more;
Wherein, X is a haloid element, and R1 is the C that halogen replaces or do not have replacement
1～C
3Alkyl, Ar1 is phenyl or C
1～C
3The phenyl that replaces of alkyl, naph is the cycloalkanes acidic group, P204 is a di (isooctyl) phosphate, P507 is the different monooctyl ester of mono phosphoric acid ester; R2 is the alkyl of C1～C11, and Ar2 is a phenyl; Ln is a rare earth metal, is selected from the periodic table of elements in the IIIB family in 15 lanthanon, scandium or the yttriums one or more.
3, poly(lactic acid) according to claim 2 is characterized in that described rare earth compound C1 is selected from rare earth oxide Ln
2O
3, rare earth halide LnX
3, rare earth sulfonate Ln (R1SO
3)
3Or Ln (Ar1SO
3)
3Or rare earth carboxylate Ln (R2COO)
3Or Ln (Ar2COO)
3In one or more;
Wherein X is a chlorion, and R1 is a trifluoromethyl, Ar1 be dodecane for phenyl, R2 is undecyl or 2-ethyl pentyl group, Ar2 is a phenyl, Ln is a rare earth metal, is selected from the periodic table of elements in the IIIB family in 15 lanthanon, scandium or the yttriums one or more.
4,, it is characterized in that described rare earth metal Ln is lanthanum La, praseodymium Pr, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er or yttrium Y according to claim 2 or 3 described poly(lactic acid).
5, poly(lactic acid) according to claim 4 is characterized in that described rare earth metal Ln is lanthanum La, neodymium Nd, samarium Sm, europium Eu or erbium Er.
6, poly(lactic acid) according to claim 1 is characterized in that described sulfoacid compound C2 is aliphatic sulfonic R3SO
3H or aromatic sulphonic acid Ar3SO
3H; Wherein R3 is the C that halogen replaces or do not have replacement
1～C
3Alkyl, Ar3 for do not have to replace, C
1～C
3The phenyl that alkyl replaces or halogen replaces.
7, poly(lactic acid) according to claim 6 is characterized in that described sulfoacid compound C2 is selected from one or more in methylsulfonic acid, ethyl sulfonic acid, 1-propyl sulfonic acid, Phenylsulfonic acid, tosic acid, p-chlorobenzenesulfonic acid or the trifluoromethanesulfonic acid.
8, poly(lactic acid) according to claim 1 is characterized in that rare earth compound C1 is 200～70000ppm of poly(lactic acid) quality; Sulfoacid compound C2 is 0～50000ppm of poly(lactic acid) quality.
9, poly(lactic acid) according to claim 8 is characterized in that rare earth compound C1 is 1000～20000ppm of poly(lactic acid) quality; Sulfoacid compound C2 is 1000～10000ppm of poly(lactic acid) quality.
10, a kind of method for preparing the described poly(lactic acid) of claim 1, it is characterized in that mixture or their oligopolymer with L-lactic acid, D-lactic acid, L-lactic acid and D-lactic acid are raw material, add rare earth compound C1 or add rare earth compound C1 simultaneously and sulfoacid compound C2 as catalyzer, carry out melt polycondensation reaction, promptly obtain the poly(lactic acid) product.
11, the method for preparing poly(lactic acid) according to claim 9 is characterized in that in the melt polycondensation reaction: condensation temp is 100 ℃～200 ℃; Its condensation pressure is along with the process of reaction reduces gradually, and original pressure is a normal atmosphere, and resulting pressure is 0.1KPa～6Kpa, perhaps directly reacts under the pressure of 0.1KPa～6Kpa; The condensation time is 3h～20h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448737A (en) * | 2014-10-17 | 2015-03-25 | 济南大学 | Carboxylic acid rare earth cross-linked PLA biodegradable plastic and preparation thereof |
| CN105504237A (en) * | 2016-02-25 | 2016-04-20 | 新疆康润洁环保科技股份有限公司 | Polylactic acid synthesis technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005187626A (en) * | 2003-12-25 | 2005-07-14 | Musashino Chemical Laboratory Ltd | Manufacturing process of polylactic acid stereo complex body |
| CN1831027A (en) * | 2005-03-10 | 2006-09-13 | 江苏九鼎新材料股份有限公司 | Catalyst for producing polylactic resin and its prodn. process |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448737A (en) * | 2014-10-17 | 2015-03-25 | 济南大学 | Carboxylic acid rare earth cross-linked PLA biodegradable plastic and preparation thereof |
| CN105504237A (en) * | 2016-02-25 | 2016-04-20 | 新疆康润洁环保科技股份有限公司 | Polylactic acid synthesis technology |
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