CN105623211A - Polylactic acid composition and preparation method thereof - Google Patents
Polylactic acid composition and preparation method thereof Download PDFInfo
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- CN105623211A CN105623211A CN201410589201.XA CN201410589201A CN105623211A CN 105623211 A CN105623211 A CN 105623211A CN 201410589201 A CN201410589201 A CN 201410589201A CN 105623211 A CN105623211 A CN 105623211A
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Abstract
The invention discloses a polylactic acid composition. The composition contains polylactic acid and an aliphatic-aromatic-polylactic acid copolyester product, wherein the content of metal elements in the aliphatic-aromatic-polylactic acid copolyester product is 0.02wt% or below. The invention also provides a preparation method of the composition. The aliphatic-aromatic-polylactic acid copolyester product has the characteristics of good flexibility, good compatibility with polylactic acid, and maintenance of the transparency and the degradation performance of polylactic acid, and allows the polylactic acid composition to have high use safety due to low content of the metal elements.
Description
Technical field
The present invention relates to a kind of poly (lactic acid) composition and preparation method thereof.
Background technology
It is known that polylactic acid is as a kind of Green Polymer Material, owing to it has biogenetic derivation, therefore Efforts To Develop polylactic acid industry can alleviate the pressure to fossil resources, and it also has benifit for alleviating greenhouse effect. But poly-lactic acid material character is more crisp, toughness is not enough, and therefore polylactic acid carries out the toughness reinforcing important directions being to improve polylactic acid performance. Wherein, adopting polylactic acid and other polyester polymers blended is the common method of plasticizing polylactic acid. Generally, polylactic acid is blended into other polyester components, the mechanical property of polylactic acid can be improved, remain in that the degradability of polylactic acid, such as polylactic acid and caprolactone system, polylactic acid/aliphatic-aromatic copolyester, polylactic acid/aliphatic polyester, polylactic acid/poly-hydroxy fatty acid etc. simultaneously.
Wherein, aliphatic-aromatic copolyester is a kind of potential polyester material, has good mechanical property, it is possible to degraded by compost, and part material has biogenetic derivation, for alleviating fossil resources pressure, alleviates greenhouse effect all beneficial. It is incorporated in polylactic acid in the way of blended, it is possible to the effective character improving polylactic acid, for instance BASF AG is by by ecoflex and polylactic acid blend, it is possible to obtain the good product of performance. But the compatibility of polylactic acid and aliphatic-aromatic copolyester is also bad, the product of simple blend can show respective glass transition temperature on DSC, therefore the blended of the two can not reach desirable effect, it usually needs adds compatilizer and improves blended situation.
Summary of the invention
The problem that it is an object of the invention to overcome existing polylactic acid and other polyester blend poor compatibility, it is provided that a kind of poly (lactic acid) composition with excellent compatibility and preparation method thereof.
Generally, lactide polymerization is adopted to prepare polylactic acid copolyesters, it is required for additionally adding the catalyst needed for lactide ring-opening polymerisation, such as the compound containing transition metal such as metallic zinc or stannum classes, so that obtained polylactic acid copolyesters remains the metallic element of higher amount, the safety in utilization of its product there is large effect. But, the inventors found that, if the aliphatic-aromatic copolymer that end is hydroxyl adopting the present invention causes lactide and copolymerized therewith, when utilizing the terminal hydroxyl of aliphatic-aromatic copolymer, can under the initiation of the rare earth-Titanium series catalyst of less consumption, obtain a kind of poly-lactic acid products that aliphatic-aromatic is copolymer-modified, i.e. aliphatic-aromatic-polylactic acid copolyesters product. Namely rare earth-the Titanium series catalyst adopting less consumption can obtain the polydactyl acid product of less tenor, and more make inventor surprisingly, this aliphatic-aromatic-polylactic acid copolyesters product also has extraordinary pliability, when the poly (lactic acid) composition that such aliphatic-aromatic-polylactic acid copolyesters product and polylactic acid carry out blending extrusion gained had both had the good compatibility, polylactic acid fragility defect originally can be overcome again. Thus completing the present invention.
Thus, the present invention provides a kind of poly (lactic acid) composition, and said composition contains polylactic acid and aliphatic-aromatic-polylactic acid copolyesters product, and wherein, in described aliphatic-aromatic-polylactic acid copolyesters product, metal element content is below 0.02 weight %; Further, the preparation method of described aliphatic-aromatic-polylactic acid copolyesters product comprises the following steps:
(1) under the existence of Titanium series catalyst, component a, component b and component c are carried out esterification;
(2) under vacuum, the esterification reaction mixture of gained in step (1) is carried out pre-polymerization;
(3) under the existence of rare-earth metal catalyst, the prepolymerization reaction mixture of gained in step (2) is carried out polycondensation reaction, obtain the product of aliphatic-aromatic copolymer, wherein, in the product of described aliphatic-aromatic copolymer, the content of described Titanium series catalyst is 0.04-0.08 weight %, and the content of described rare-earth metal catalyst is 0.022-0.1 weight %;
(4) product of the aliphatic-aromatic copolymer of step (3) gained and lactide monomer are carried out copolyreaction, wherein, the described product of aliphatic-aromatic copolymer and the consumption of lactide monomer make: with the gross weight of lactide monomer for benchmark, the content of described Titanium series catalyst is 0.017-0.08 weight %, and the content of described rare-earth metal catalyst is 0.0033-0.1 weight %;
Wherein, described component a is C8-C20Aromatic acid, described C8-C20The anhydride of aromatic acid and described C8-C20Aromatic acid ester in one or more; Described component b is C2-C10Aliphatic dihydroxy alcohol and/or C3-C10Cycloaliphatic diols; Described component c is C2-C20Aliphatic dibasic acid, C3-C10Cycloaliphatic diacid and their anhydride in one or more.
The preparation method that present invention also offers above-mentioned poly (lactic acid) composition, the method includes:
(1) under the existence of Titanium series catalyst, component a, component b and component c are carried out esterification;
(2) under vacuum, the esterification reaction mixture of gained in step (1) is carried out pre-polymerization;
(3) under the existence of rare-earth metal catalyst, the prepolymerization reaction mixture of gained in step (2) is carried out polycondensation reaction, obtain the product of aliphatic-aromatic copolymer, wherein, in the product of described aliphatic-aromatic copolymer, the content of described Titanium series catalyst is 0.04-0.08 weight %, and the content of described rare-earth metal catalyst is 0.022-0.1 weight %;
(4) product of the aliphatic-aromatic copolymer of step (3) gained and lactide monomer are carried out copolyreaction, wherein, the described product of aliphatic-aromatic copolymer and the consumption of lactide monomer make: with the gross weight of lactide monomer for benchmark, the content of described Titanium series catalyst is 0.017-0.08 weight %, and the content of described rare-earth metal catalyst is 0.0033-0.1 weight %; In the aliphatic-aromatic of described copolyreaction gained-polylactic acid copolyesters product, metal element content is below 0.02 weight %;
(5) polylactic acid and step (4) gained aliphatic-aromatic-polylactic acid copolyesters product are carried out blending extrusion,
Wherein, described component a is C8-C20Aromatic acid, described C8-C20The anhydride of aromatic acid and described C8-C20Aromatic acid ester in one or more; Described component b is C2-C10Aliphatic dihydroxy alcohol and/or C3-C10Cycloaliphatic diols; Described component c is C2-C20Aliphatic dibasic acid, C3-C10Cycloaliphatic diacid and their anhydride in one or more.
Poly (lactic acid) composition provided by the invention, it is actually the polylactic acid of a kind of blending and modifying, which employs the aliphatic-aromatic obtained by step (1)-(4)-polylactic acid copolyesters product, and it is carried out blended with common polylactic acid, owing to described aliphatic-aromatic-polylactic acid copolyesters product has good pliability, can be compatible well with polylactic acid, and keep transparency and the degradation property of polylactic acid, simultaneously because described aliphatic-aromatic-polylactic acid copolyesters product has relatively low metal element content, poly (lactic acid) composition of the present invention is made to have higher safety in utilization.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail. It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
The present invention provides a kind of poly (lactic acid) composition, and said composition contains polylactic acid and aliphatic-aromatic-polylactic acid copolyesters product, and wherein, in described aliphatic-aromatic-polylactic acid copolyesters product, metal element content is below 0.02 weight %; Further, the preparation method of described aliphatic-aromatic-polylactic acid copolyesters product comprises the following steps:
(1) under the existence of Titanium series catalyst, component a, component b and component c are carried out esterification;
(2) under vacuum, the esterification reaction mixture of gained in step (1) is carried out pre-polymerization;
(3) under the existence of rare-earth metal catalyst, the prepolymerization reaction mixture of gained in step (2) is carried out polycondensation reaction, obtain the product of aliphatic-aromatic copolymer, wherein, in the product of described aliphatic-aromatic copolymer, the content of described Titanium series catalyst is 0.04-0.08 weight %, and the content of described rare-earth metal catalyst is 0.022-0.1 weight %;
(4) product of the aliphatic-aromatic copolymer of step (3) gained and lactide monomer are carried out copolyreaction, wherein, the described product of aliphatic-aromatic copolymer and the consumption of lactide monomer make: with the gross weight of lactide monomer for benchmark, the content of described Titanium series catalyst is 0.017-0.08 weight %, and the content of described rare-earth metal catalyst is 0.0033-0.1 weight %;
Wherein, described component a is C8-C20Aromatic acid, described C8-C20The anhydride of aromatic acid and described C8-C20Aromatic acid ester in one or more; Described component b is C2-C10Aliphatic dihydroxy alcohol and/or C3-C10Cycloaliphatic diols; Described component c is C2-C20Aliphatic dibasic acid, C3-C10Cycloaliphatic diacid and their anhydride in one or more.
According to the present invention, described polylactic acid is not particularly limited, can be various polylactic acid commonly used in the art, but in order to compatible with the aliphatic-aromatic of gained of the present invention-polylactic acid copolyesters product better, under preferable case, the weight average molecular weight that described polylactic acid has is 8-20 ten thousand, for instance can be the REVODE210 trade mark etc. of 4032 trades mark of natureworks company, Hai Zheng company.
According to the present invention, in described poly (lactic acid) composition, the consumption of described polylactic acid and aliphatic-aromatic-polylactic acid copolyesters product is not particularly limited, as long as enabling to polylactic acid and aliphatic-aromatic-polylactic acid copolyesters product having the better compatibility, and gained poly (lactic acid) composition is functional, under preferable case, the weight ratio of described polylactic acid and aliphatic-aromatic-polylactic acid copolyesters product is 100:10-100, it is more preferably 100:15-60, is further preferably 100:25-50.
According to the invention it is preferred in situation, with the gross weight of described poly (lactic acid) composition for benchmark, the content of described polylactic acid is 50-92 weight %, the content of described aliphatic-aromatic-polylactic acid copolyesters product is 8-50 weight %. It is highly preferred that with the gross weight of described poly (lactic acid) composition for benchmark, the content of described polylactic acid is 65-87 weight %, the content of described aliphatic-aromatic-polylactic acid copolyesters product is 13-35 weight %.
According to the present invention, described aliphatic-aromatic-polylactic acid copolyesters product is prepared by step (1)-(4). Wherein, step (1)-(3) are by the product of prepared aliphatic-aromatic copolymer, this product contains substantial amounts of aliphatic-aromatic copolymer and a small amount of Titanium series catalyst and rare-earth metal catalyst, it will be appreciated by those skilled in the art that the product for aliphatic-aromatic copolymer is made up of aliphatic-aromatic copolymer and catalyst. Under preferable case, in this product, the content of described Titanium series catalyst is preferably 0.04-0.073 weight %, more preferably 0.05-0.073 weight %. Preferably, the content of described rare-earth metal catalyst is 0.025-0.095 weight %, more preferably 0.028-0.055 weight %.
According to the invention it is preferred in situation, the mol ratio of the consumption of the consumption of the Titanium series catalyst in step (1) and the rare-earth metal catalyst in the polycondensation reaction of step (3) is 1:0.4-1, more preferably 1:05-1.
Wherein, the construction unit of described aliphatic-aromatic copolymer has structure shown in formula (1):
Wherein, Ar is the group with phenyl ring, naphthalene nucleus or anthracene nucleus; M is preferably the integer of 1-20; N is preferably the integer of 1-16; T is preferably the integer of 1-20; X can be the integer of 1-100, it is preferred to the integer of 15-60; Y can be the integer of 1-100, it is preferred to the integer of 15-60.
Under preferable case, Ar is following aryl:
Wherein, R1��R2��R3��R4��R5And R6It is each independently hydrogen, the alkyl of C1-C4, F, Cl ,-NO2,-CN or-OR7, wherein, R7Alkyl for C1-C4.
In most preferred situation, Ar isWherein, R1And R2Same as above.
According to the present invention, in order to obtain the better transparency and flexility, it is preferable that in situation, the weight average molecular weight of described aliphatic-aromatic copolymer is 3000-40000, and molecular weight distribution index is 1.2-2.5. It is highly preferred that the weight average molecular weight of described aliphatic-aromatic copolymer is 6000-35000, molecular weight distribution index is 1.4-2.2.
According to the present invention, in order to obtain the more excellent aliphatic-aromatic copolymer of flexility and degradation property, under preferable case, described component a be M-phthalic acid, p-phthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4 '-biphenyl dicarboxylic acid and 3, one or more in 4 '-biphenyl dicarboxylic acid, be more preferably in p-phthalic acid, M-phthalic acid and phthalic acid one or more, be further preferably p-phthalic acid.
Under preferable case, described component b is one or more in ethylene glycol, diethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexane diol and norbornane dimethanol, be more preferably in butanediol, hexanediol and cyclohexane diol one or more, be further preferably butanediol.
Under preferable case, described component c be succinic acid, succinic anhydride, adipic acid, adipic anhydride, Azelaic Acid, decanedioic acid, dodecanedioic acid, 1,4-cyclohexane diacid, 1,2, one or more in 4,5-hexamethylene tetracarboxylic dianhydrides and norbornane diacid, more preferably succinic acid, adipic acid and 1, one or more in 4-cyclohexane diacid, are further preferably adipic acid.
According to the present invention, although the reaction that component a, component b and component c carry out step (1)-(3) can obtain the product of described aliphatic-aromatic copolymer, so that component a, component b and component c react more abundant and obtain has the aliphatic-aromatic copolymer that biodegradability is excellent, under preferable case, the mol ratio of described component a, component b and component c is 1:(2-5): (0.8-3), it is more preferably 1:(2-4.5): (0.8-2.5), further it is preferably 1:(2-4.4): (1-1.5).
According to the present invention, the consumption of described Titanium series catalyst is not particularly limited, as long as can the carrying out of described esterification in catalytic step (1), and promote aliphatic-aromatic copolymer and lactide monomer copolymerization, but in order to namely there be enough amounts to meet the carrying out of described esterification, and promote aliphatic-aromatic copolymer and lactide monomer copolymerization, will not give again in the copolymer-modified poly-lactic acid products of the aliphatic-aromatic of aliphatic-aromatic copolymer and lactide monomer copolymerization and introduce too much metal element content, under preferable case, with described component a, the integral molar quantity of component b and component c is benchmark, in step (1), the consumption of described Titanium series catalyst is 0.01-0.04mol%, it is more preferably 0.016-0.029mol%.
According to the present invention, in like manner, in order to namely there be enough amounts to meet the carrying out of polycondensation reaction described in step (3), and promote aliphatic-aromatic copolymer and lactide monomer copolymerization, will not give again in the copolymer-modified poly-lactic acid products of the aliphatic-aromatic of aliphatic-aromatic copolymer and lactide monomer copolymerization and introduce too much metal element content, under preferable case, with the integral molar quantity of described component a, component b and component c for benchmark, the consumption of described rare-earth metal catalyst is 0.005-0.03mol%, more preferably 0.008-0.015mol%.
According to the invention it is preferred in situation, described Titanium series catalyst is one or more in butyl titanate titanium isopropoxide, titanium dioxide and titanium tetrachloride, more preferably one or more in butyl titanate, titanium dioxide and titanium isopropoxide. Described Titanium series catalyst can be commercially available product, it is also possible to being prepared by conventional method, its preparation method does not repeat them here.
According to the present invention, under preferable case, described rare-earth metal catalyst is one or more in lanthanum acetylacetone, lanthanum chloride, isopropoxy neodymium, 2,6-dibutyl-4-methylenedioxy phenoxy neodymiums and Lanthanum Stearate, more preferably one or more in lanthanum acetylacetone, isopropoxy neodymium and Lanthanum Stearate. Described rare-earth metal catalyst can be commercially available product, conventional method can also be passed through prepare, such as the method by recording in document " InorganicChemistry1970; 9; 2505, J.Chem.Soc.Chem.Commun.1983,1499 " prepares, the detailed process of its preparation method, does not repeat them here.
According to the invention it is preferred in situation, the condition of described esterification includes: reaction temperature is 150-230 DEG C, the response time is 2-7h. More preferably in situation, the esterification in step (1) includes: component a and component b first carries out the first esterification, then with component c, the material after the first esterification is carried out the second esterification. Wherein, the condition of described first esterification includes: reaction temperature is 150-230 DEG C, and the response time is 1-3h. The condition of described second esterification includes: reaction temperature is 180-220 DEG C, and the response time is 1-4h. It is highly preferred that the condition of described first esterification includes: reaction temperature is 180-200 DEG C, the response time is 2-3h. The condition of described second esterification includes: reaction temperature is 200-220 DEG C, and the response time is 2-4h.
According to the invention it is preferred in situation, in step (2), the condition of described pre-polymerization includes: absolute pressure is below 500Pa, and reaction temperature is 200-250 DEG C, and the response time is 1-6h. Being more preferably, the condition of described pre-polymerization includes: absolute pressure is below 400Pa, and reaction temperature is 200-240 DEG C, and the response time is 1-3h.
Under preferable case, in step (3), the condition of described polycondensation reaction includes: below 400Pa under absolute pressure, and reaction temperature is 220-250 DEG C, and the response time is 1-5h. It is highly preferred that the condition of described polycondensation reaction includes: absolute pressure is below 400Pa, and reaction temperature is 220-240 DEG C, the response time is 1-2h.
According to the invention it is preferred in situation, the reaction of above-mentioned steps (1)-(3) carries out all under nitrogen protection.
According to the present invention, the product prepared through above-mentioned steps (1)-(3) is carried out vacuum volatilization dry, remove unreacted monomer etc., thus the product of the aliphatic-aromatic copolymer obtained in the present invention, therefore, the product of described aliphatic-aromatic copolymer remains with most catalyst in the present invention that add in step (1)-(3) course of reaction, i.e. Titanium series catalyst and rare-earth metal catalyst, and the product of described aliphatic-aromatic copolymer is nearly all described aliphatic-aromatic copolymer except Titanium series catalyst and rare-earth metal catalyst. as above, it will be appreciated by those skilled in the art that the product of the aliphatic-aromatic copolymer for the present invention is made up of Titanium series catalyst and rare-earth metal catalyst and aliphatic-aromatic copolymer.
According to the present invention, the product of the aliphatic-aromatic copolymer prepared above-mentioned steps (1)-(3) carries out copolyreaction with lactide monomer in step (4), such that it is able to obtain the aliphatic-aromatic-polylactic acid copolyesters product of the present invention.
Wherein, a small amount of Titanium series catalyst and rare-earth metal catalyst is carried due to the product of aliphatic-aromatic copolymer, carry out under the Titanium series catalyst and rare-earth metal catalyst existence of this part so that the copolyreaction of step (4) is actually, under preferable case, the described product of aliphatic-aromatic copolymer and the consumption of lactide monomer make: with the gross weight of lactide monomer for benchmark, the content of described Titanium series catalyst is 0.02-0.073 weight %, and the content of described rare-earth metal catalyst is 0.01-0.095 weight %.
It addition, the consumption of the product of described aliphatic-aromatic copolymer and described lactide monomer can realize the purpose of the present invention in above-mentioned scope. It is further preferred that with the described lactide monomer of 100 weight portions for benchmark, the consumption of the product of described aliphatic-aromatic copolymer is 15-110 weight portion, more preferably 17-100 weight portion, further it is preferably 35-100 weight portion.
According to the invention it is preferred in situation, in step (4), the condition of described copolyreaction includes: reaction temperature is 150-190 DEG C, the response time is 2-5h. It is highly preferred that the condition of described copolyreaction includes: reaction temperature is 170-185 DEG C, the response time is 2.5-5h.
Wherein, it is preferable that in situation, described copolyreaction carries out in a nitrogen atmosphere, and just proceeds by copolyreaction after first passing into nitrogen 1-5h to reaction system.
According to the invention it is preferred in situation, after described polyreaction terminates, add retarder thinner and be diluted, add methanol and precipitate, to obtain the precipitation of aliphatic-aromatic-polylactic acid copolyesters product. Described retarder thinner can be one or more in chloroform, dichloromethane, oxolane and DMF, it is preferred to one or more in chloroform, dichloromethane and oxolane.
Catalyst it is not additionally added so that containing very small amount of metallic element in the aliphatic-aromatic of gained-polylactic acid copolyesters product due in the copolyreaction that the product of the aliphatic-aromatic copolymer in step (4) and lactide monomer in the present invention carry out. Such as, the metal element content in described aliphatic-aromatic-polylactic acid copolyesters product is below 0.02 weight %, it is preferred to 0.002-0.015 weight %, is further preferably 0.004-0.008 weight %.
According to the present invention, the copolyreaction that the product of the aliphatic-aromatic copolymer in step (4) and lactide monomer carry out is a kind of random copolymerization, namely between aliphatic-aromatic copolymer therein, between aliphatic-aromatic copolymer and lactide monomer, can be polymerized between lactide monomer, and the product of they polymerizations can also be polymerized again, thus the aliphatic-aromatic of gained of the present invention-polylactic acid copolyesters product is also the atactic polymer of a kind of polylactic acid copolymer-modified through aliphatic-aromatic. Further, when additionally not adding catalyst, this aliphatic-aromatic of gained-polylactic acid copolyesters product has good pliability, and metal element content is low.
The preparation method that present invention also offers above-mentioned poly (lactic acid) composition, the method includes:
(1) under the existence of Titanium series catalyst, component a, component b and component c are carried out esterification;
(2) under vacuum, the esterification reaction mixture of gained in step (1) is carried out pre-polymerization;
(3) under the existence of rare-earth metal catalyst, the prepolymerization reaction mixture of gained in step (2) is carried out polycondensation reaction, obtain the product of aliphatic-aromatic copolymer, wherein, in the product of described aliphatic-aromatic copolymer, the content of described Titanium series catalyst is 0.04-0.08 weight %, and the content of described rare-earth metal catalyst is 0.022-0.1 weight %;
(4) product of the aliphatic-aromatic copolymer of step (3) gained and lactide monomer are carried out copolyreaction, wherein, the described product of aliphatic-aromatic copolymer and the consumption of lactide monomer make: with the gross weight of lactide monomer for benchmark, the content of described Titanium series catalyst is 0.017-0.08 weight %, and the content of described rare-earth metal catalyst is 0.0033-0.1 weight %; In the aliphatic-aromatic of described copolyreaction gained-polylactic acid copolyesters product, metal element content is below 0.02 weight %;
(5) polylactic acid and step (4) gained aliphatic-aromatic-polylactic acid copolyesters product are carried out blending extrusion,
Wherein, described component a is C8-C20Aromatic acid, described C8-C20The anhydride of aromatic acid and described C8-C20Aromatic acid ester in one or more; Described component b is C2-C10Aliphatic dihydroxy alcohol and/or C3-C10Cycloaliphatic diols; Described component c is C2-C20Aliphatic dibasic acid, C3-C10Cycloaliphatic diacid and their anhydride in one or more.
Wherein, step (1)-(4) are similar to aforesaid description, are not discussed here.
And the method that the blending extrusion of step (5) can adopt the conventional blending extrusion in this area, this is not had any restriction by the present invention.
By the preparation method of the poly (lactic acid) composition of the present invention, by obtaining the product of a kind of polylactic acid modified by blending method, it is the poly (lactic acid) composition of the present invention. This poly (lactic acid) composition both can keep good biological degradation rate, the hypotoxicity that polylactic acid has, and can obtain again higher pliability.
Hereinafter will be described the present invention by embodiment.
In following catalyst preparation example, preparation example, preparation comparative example, embodiment and comparative example,
In its aliphatic-aromatic-polylactic acid copolyesters, polylactic acid chain segment/copolyesters weight ratio is measured by magnetic nuclear resonance method;
Weight average molecular weight and molecular weight distributing index adopt gel permeation chromatography (GPC) to measure, wherein, with oxolane (THF) for solvent, at Waters-208 (band Waters2410RI detector, 1.5mL/min flow velocity, 30 DEG C) instrument to be measured, molecular weight is with the linear polystyrene standards calibration of single dispersing;
Hot strength and fracture tensile strength are according to the method measurement recorded in GB/T1040.2-2006;
Biodegradability is to carry out detecting according to the method recorded in GB/T19275-2003, mainly test post-consumer polymer sample is accounted for the percentage by weight of test prepolymer sample to represent biological degradation rate relative to the mass loss of the polymer samples before test;
The toxicity of biodegradable product is to carry out detecting according to the method recorded in DIN38412-30-1989.
Catalyst preparation example 1
Lanthanum chloride 9.37mmol is dissolved in the water of 50mL, is then added in the aqueous solution of the acetylacetone,2,4-pentanedione containing 56.2mmol, at room temperature stirs, adjust pH to neutral by adding the aqueous solution of 2NKOH. Reactant mixture stirs, and filters, dry at 60 DEG C of vacuum, obtains lanthanum acetylacetone 4g.
Catalyst preparation example 2
Lanthanum chloride 9.37mmol is dissolved in the water of 50mL, is then added in the aqueous solution of the sodium stearate containing 20mmol, at room temperature stirs, adjust pH to neutral by adding the aqueous solution of 2NHCl. Reactant mixture stirs, and filters, dry at 60 DEG C of vacuum, obtains Lanthanum Stearate 11g.
Preparation example 1
By 2.2mol p-phthalic acid, 5mol butanediol and 1.6mmol butyl titanate (purchased from Beijing chemical reagents corporation; chemical pure) join in reactor; and under nitrogen protection; it is heated with stirring to backflow; reaction temperature controls at 180 DEG C; and collect the water steamed, treat that water almost collects complete (about reacting 2h). It is possible to additionally incorporate 2.5mol succinic acid in system, continue to be heated with stirring to backflow, reaction temperature controls at 200 DEG C, collects the water steamed, almost collects complete (about reacting 2h) to water. Then, by this system temperature be 230 DEG C, absolute pressure be 400Pa when pre-polymerization be about 1h. Finally, 0.85mmol lanthanum acetylacetone is added in this system, temperature be 230 DEG C, absolute pressure be maintained at below 200Pa when, polycondensation is about 1h, is dried the aliphatic-aromatic copolyester P1 of the white obtaining 750g by vacuum volatilization, and its weight average molecular weight is 10000, molecular weight distributing index is 2.2, and in this copolyesters P1, the content of butyl titanate is 0.060 weight %, and the content of lanthanum acetylacetone is 0.041 weight %.
L-lactide monomer (LLA) and the 30g aliphatic-aromatic copolyester P1 of 80g is added separately in reactor, and (total amount of aliphatic-aromatic copolymer p 1 and lactide monomer is benchmark, the content of butyl titanate is 0.016 weight %, the content of lanthanum acetylacetone is 0.011 weight %), 5h will be purged with high pure nitrogen after mix homogeneously, under nitrogen atmosphere reaction bulb is placed at 170 DEG C and reacts after 5h, cooling, with chloroform dilution mixture thing, and precipitate in absolute methanol, gained precipitate is aliphatic-aromatic-polylactic acid copolyesters product A 1 (97g, wherein, the content of titanium is 0.0022 weight %, the content of lanthanum is 0.0036 weight %), its lactide/copolyesters weight ratio, weight average molecular weight, molecular weight distributing index, hot strength and fracture elongation rate are as shown in table 1.
Preparation example 2
2.2mol p-phthalic acid, 5mol butanediol and 1.6mmol butyl titanate are joined in reactor; and under nitrogen protection, it being heated with stirring to backflow, reaction temperature controls at 200 DEG C; and collect the water steamed, treat that water almost collects complete (about reacting 2h). It is possible to additionally incorporate 2.5mol succinic acid in system, continue to be heated with stirring to backflow, reaction temperature controls at 220 DEG C, collects the water steamed, almost collects complete (about reacting 2h) to water. Then, by this system temperature be 240 DEG C, absolute pressure be 400Pa when pre-polymerization be about 1h. Finally, 0.85mmol Lanthanum Stearate is added in this system, temperature be 240 DEG C, absolute pressure be maintained at below 200Pa when, polycondensation is about 1.5h, and the purification process dried by vacuum volatilization obtains the aliphatic-aromatic copolyester P2 of the white of 700g, and its weight average molecular weight is 31000, molecular weight distributing index is 1.67, and in this copolyesters P2, the content of butyl titanate is 0.041 weight %, and the content of Lanthanum Stearate is 0.025 weight %.
L-lactide monomer (LLA) and the 30g aliphatic-aromatic copolyester P2 of 80g is added separately in reactor, and (total amount of aliphatic-aromatic copolymer p 2 and lactide monomer is benchmark, the content of butyl titanate is 0.011 weight %, the content of Lanthanum Stearate is 0.0068 weight %), 5h will be purged with high pure nitrogen after mix homogeneously, under nitrogen atmosphere reaction bulb is placed at 170 DEG C and reacts after 5h, cooling, with chloroform dilution mixture thing, and precipitate in absolute methanol, gained precipitate is aliphatic-aromatic-polylactic acid copolyesters product A 2 (95g, wherein, the content of titanium is 0.0016 weight %, the content of lanthanum is 0.0025 weight %), its lactide/copolyesters weight ratio, weight average molecular weight, molecular weight distributing index, hot strength and fracture elongation rate are as shown in table 1.
Preparation comparative example 1
Adopt preparation method described in example 1, institute the difference is that, the stannous octoate adding 82mg that takes a step forward is reacted as catalyst in L-lactide monomer (LLA) and aliphatic-aromatic copolyester P1, gained precipitate is aliphatic-aromatic-polylactic acid copolyesters product DA1 (106g, wherein, the content of titanium is 0.0015 weight %, the content of lanthanum is 0.003 weight %, the content of stannum is 0.02 weight %), its lactide/copolyesters weight ratio, weight average molecular weight, molecular weight distributing index, hot strength and fracture elongation rate are as shown in table 1.
Table 1
Embodiment 1-3
The present embodiment is for illustrating the poly (lactic acid) composition of the present invention.
200g polylactic acid (natureworks company trade mark 4042D) is joined in double screw extruder with the aliphatic-aromatic of 100g, 50g and 120g-polylactic acid copolyesters product A 1 respectively, Homogeneous phase mixing is also extruded, wherein, from charging aperture to extrusion, each section of temperature is followed successively by 100 DEG C, 170 DEG C, 170 DEG C, 160 DEG C. The poly (lactic acid) composition that obtains of extrusion carries out biological degradation rate, the toxicity of catabolite is measured, and carries out hot strength and the mensuration of break-draw rate after making the sample panel of 15 �� 15 �� 2mm, and its result is in Table 2.
Embodiment 4-5
The present embodiment is for illustrating the poly (lactic acid) composition of the present invention.
200g polylactic acid (natureworks company trade mark 4042D) is joined in double screw extruder with the aliphatic-aromatic of 100g and 120g-polylactic acid copolyesters product A 2 respectively, Homogeneous phase mixing is also extruded, wherein, from charging aperture to extrusion, each section of temperature is followed successively by 100 DEG C, 170 DEG C, 170 DEG C, 160 DEG C. The poly (lactic acid) composition that obtains of extrusion carries out biological degradation rate, the toxicity of catabolite is measured, and carries out hot strength and the mensuration of break-draw rate after making the sample panel of 15 �� 15 �� 2mm, and its result is in Table 2.
Embodiment 6
According to the method described in embodiment 1, institute the difference is that, the consumption of aliphatic-aromatic-polylactic acid copolyesters product A 1 is 35g, the poly (lactic acid) composition that extrusion obtains carries out biological degradation rate, the toxicity of catabolite is measured, and after making the sample panel of 15 �� 15 �� 2mm, carrying out hot strength and the mensuration of break-draw rate, its result is in Table 2.
Embodiment 7
According to the method described in embodiment 1, institute the difference is that, the consumption of aliphatic-aromatic-polylactic acid copolyesters product A 1 is 180g, the poly (lactic acid) composition that extrusion obtains carries out biological degradation rate, the toxicity of catabolite is measured, and after making the sample panel of 15 �� 15 �� 2mm, carrying out hot strength and the mensuration of break-draw rate, its result is in Table 2.
Comparative example 1
According to the method described in embodiment 1, institute the difference is that, the aliphatic-aromatic copolyester P1 adopting 100g replaces aliphatic-aromatic-polylactic acid copolyesters product A 1, the poly (lactic acid) composition that extrusion obtains carries out the toxicity test of biological degradation rate, catabolite, and after making the sample panel of 15 �� 15 �� 2mm, carrying out hot strength and the mensuration of break-draw rate, its result is in Table 2.
Comparative example 2
According to the method described in embodiment 4, institute the difference is that, the aliphatic-aromatic copolyester P2 adopting 100g replaces aliphatic-aromatic-polylactic acid copolyesters product A 2, the poly (lactic acid) composition that extrusion obtains carries out the toxicity test of biological degradation rate, catabolite, and after making the sample panel of 15 �� 15 �� 2mm, carrying out hot strength and the mensuration of break-draw rate, its result is in Table 2.
Comparative example 3
According to the method described in embodiment 1, institute the difference is that, aliphatic-aromatic-polylactic acid copolyesters product the DA1 adopting 100g replaces A1, the poly (lactic acid) composition that extrusion obtains carries out the toxicity test of biological degradation rate, catabolite, and after making the sample panel of 15 �� 15 �� 2mm, carrying out hot strength and the mensuration of break-draw rate, its result is in Table 2.
Table 2
| Copolyesters | Hot strength (MPa) | Elongation at break (%) | Biological degradation rate | The toxicity of catabolite |
| Embodiment 1 | 25.6 | 51 | 100% | Nontoxic |
| Embodiment 2 | 30 | 26 | 100% | Nontoxic |
| Embodiment 3 | 21.3 | 120 | 100% | Nontoxic |
| Embodiment 4 | 29.5 | 44 | 100% | Nontoxic |
| Embodiment 5 | 22 | 84 | 100% | Nontoxic |
| Embodiment 6 | 35.2 | 25 | 100% | Nontoxic |
| Embodiment 7 | 22.7 | 80 | 100% | Nontoxic |
| Comparative example 1 | 26.9 | 18 | 100% | Nontoxic |
| Comparative example 2 | 35 | 15 | 100% | Nontoxic |
| Comparative example 3 | 16.5 | 13 | 100% | Nontoxic |
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can being carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, it is possible to be combined by any suitable mode, in order to avoid unnecessary repetition, various possible compound modes are no longer illustrated by the present invention separately.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (15)
1. a poly (lactic acid) composition, it is characterised in that said composition contains polylactic acid and aliphatic-aromatic-polylactic acid copolyesters product, wherein, in described aliphatic-aromatic-polylactic acid copolyesters product, metal element content is below 0.02 weight %; Further, the preparation method of described aliphatic-aromatic-polylactic acid copolyesters product comprises the following steps:
(1) under the existence of Titanium series catalyst, component a, component b and component c are carried out esterification;
(2) under vacuum, the esterification reaction mixture of gained in step (1) is carried out pre-polymerization;
(3) under the existence of rare-earth metal catalyst, the prepolymerization reaction mixture of gained in step (2) is carried out polycondensation reaction, obtain the product of aliphatic-aromatic copolymer, wherein, in the product of described aliphatic-aromatic copolymer, the content of described Titanium series catalyst is 0.04-0.08 weight %, and the content of described rare-earth metal catalyst is 0.022-0.1 weight %;
(4) product of the aliphatic-aromatic copolymer of step (3) gained and lactide monomer are carried out copolyreaction, wherein, the described product of aliphatic-aromatic copolymer and the consumption of lactide monomer make: with the gross weight of lactide monomer for benchmark, the content of described Titanium series catalyst is 0.017-0.08 weight %, and the content of described rare-earth metal catalyst is 0.0033-0.1 weight %;
Wherein, described component a is C8-C20Aromatic acid, described C8-C20The anhydride of aromatic acid and described C8-C20Aromatic acid ester in one or more; Described component b is C2-C10Aliphatic dihydroxy alcohol and/or C3-C10Cycloaliphatic diols; Described component c is C2-C20Aliphatic dibasic acid, C3-C10Cycloaliphatic diacid and their anhydride in one or more.
2. compositions according to claim 1, wherein, the weight ratio of described polylactic acid and aliphatic-aromatic-polylactic acid copolyesters product is 100:10-100, it is preferred to 100:15-60, more preferably 100:25-50.
3. compositions according to claim 1 and 2, wherein, with the gross weight of described poly (lactic acid) composition for benchmark, the content of described polylactic acid is 50-92 weight %, and the content of described aliphatic-aromatic-polylactic acid copolyesters product is 8-50 weight %.
4. compositions according to claim 1, wherein, in step (4), the described product of aliphatic-aromatic copolymer and the consumption of lactide monomer make: with the gross weight of lactide monomer for benchmark, the content of described Titanium series catalyst is 0.02-0.073 weight %, and the content of described rare-earth metal catalyst is 0.01-0.095 weight %.
5. method according to claim 1, wherein, the mol ratio of the consumption of the consumption of the Titanium series catalyst in step (1) and the rare-earth metal catalyst in the polycondensation reaction of step (3) is 1:0.4-1.
6. compositions according to claim 1, wherein, described Titanium series catalyst is one or more in butyl titanate, titanium isopropoxide, titanium dioxide and titanium tetrachloride; Described rare-earth metal catalyst is one or more in lanthanum acetylacetone, lanthanum chloride, isopropoxy neodymium, 2,6-dibutyl-4-methylenedioxy phenoxy neodymium and Lanthanum Stearate.
7. compositions according to claim 1, wherein, described component a be M-phthalic acid, p-phthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acids, 4,4 '-biphenyl dicarboxylic acid and 3, one or more in 4 '-biphenyl dicarboxylic acid, it is preferred to one or more in p-phthalic acid, M-phthalic acid and phthalic acid; Described component b is one or more in ethylene glycol, diethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexane diol and norbornane dimethanol, it is preferred to one or more in butanediol, hexanediol and cyclohexane diol; Described component c be succinic acid, succinic anhydride, adipic acid, adipic anhydride, Azelaic Acid, decanedioic acid, dodecanedioic acid, 1,4-cyclohexane diacid, 1,2,4, one or more in 5-hexamethylene tetracarboxylic dianhydride and norbornane diacid, preferably one or more in succinic acid, adipic acid and Isosorbide-5-Nitrae-cyclohexane diacid.
8. compositions according to claim 1, wherein, the mol ratio of described component a, component b and component c is 1:(2-5): (0.8-3), it is preferred to 1:(2-4.5): (0.8-2.5).
9. compositions according to claim 1, wherein, with the integral molar quantity of described component a, component b and component c for benchmark, in step (1), the consumption of described Titanium series catalyst is 0.01-0.04mol%, it is preferred to 0.016-0.029mol%.
10. compositions according to claim 1, wherein, with the integral molar quantity of described component a, component b and component c for benchmark, in step (3), the consumption of described rare-earth metal catalyst is 0.005-0.03mol%, it is preferred to 0.008-0.015mol%.
11. compositions according to claim 1, wherein, the weight average molecular weight of the product of described aliphatic-aromatic copolymer is 3000-40000, and molecular weight distribution index is 1.2-2.5.
12. compositions according to claim 1, wherein, in step (1), the condition of described esterification includes: reaction temperature is 15-230 DEG C, and the response time is 2-7h; In step (2), the condition of described pre-polymerization includes: absolute pressure is below 500Pa, and reaction temperature is 200-250 DEG C, and the response time is 1-6h; In step (3), the condition of described polycondensation reaction includes: absolute pressure is below 400Pa, and reaction temperature is 220-250 DEG C, and the response time is 1-5h; In step (4), the condition of described copolyreaction includes: reaction temperature is 150-190 DEG C, and the response time is 2-5h.
13. compositions according to claim 12, wherein, in step (1), described esterification includes: component a and component b first carries out the first esterification, then with component c, the material after the first esterification is carried out the second esterification; Wherein, the condition of described first esterification includes: reaction temperature is 150-230 DEG C, and the response time is 1-3h; The condition of described second esterification includes: reaction temperature is 180-220 DEG C, and the response time is 1-4h.
14. compositions according to claim 1, wherein, in described aliphatic-aromatic-polylactic acid copolyesters product, metal element content is 0.002-0.015 weight %.
15. the preparation method of poly (lactic acid) composition described in any one in a claim 1-14, it is characterised in that the method includes:
(1) under the existence of Titanium series catalyst, component a, component b and component c are carried out esterification;
(2) under vacuum, the esterification reaction mixture of gained in step (1) is carried out pre-polymerization;
(3) under the existence of rare-earth metal catalyst, the prepolymerization reaction mixture of gained in step (2) is carried out polycondensation reaction, obtain the product of aliphatic-aromatic copolymer, wherein, in the product of described aliphatic-aromatic copolymer, the content of described Titanium series catalyst is 0.04-0.08 weight %, and the content of described rare-earth metal catalyst is 0.022-0.1 weight %;
(4) product of the aliphatic-aromatic copolymer of step (3) gained and lactide monomer are carried out copolyreaction, wherein, the described product of aliphatic-aromatic copolymer and the consumption of lactide monomer make: with the gross weight of lactide monomer for benchmark, the content of described Titanium series catalyst is 0.017-0.08 weight %, and the content of described rare-earth metal catalyst is 0.0033-0.1 weight %; In the aliphatic-aromatic of described copolyreaction gained-polylactic acid copolyesters product, metal element content is below 0.02 weight %;
(5) polylactic acid and step (4) gained aliphatic-aromatic-polylactic acid copolyesters product are carried out blending extrusion,
Wherein, described component a is C8-C20Aromatic acid, described C8-C20The anhydride of aromatic acid and described C8-C20Aromatic acid ester in one or more; Described component b is C2-C10Aliphatic dihydroxy alcohol and/or C3-C10Cycloaliphatic diols; Described component c is C2-C20Aliphatic dibasic acid, C3-C10Cycloaliphatic diacid and their anhydride in one or more.
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| CN112757520A (en) * | 2019-11-01 | 2021-05-07 | 中国石油化工股份有限公司 | Polyester granulation method |
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