CN105623211B - A kind of poly (lactic acid) composition and preparation method thereof - Google Patents
A kind of poly (lactic acid) composition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of poly (lactic acid) composition, said composition contains PLA and aliphatic aromatic PLA copolyesters product, wherein, metal element content is below 0.02 weight % in the aliphatic aromatic PLA copolyesters product.Present invention also offers the preparation method of above-mentioned composition.Because the aliphatic aromatic PLA copolyesters product has preferable pliability, can be compatible well with PLA, and keep the transparency and degradation property of PLA, simultaneously because the aliphatic aromatic PLA copolyesters product has relatively low metal element content so that poly (lactic acid) composition of the present invention has higher safety in utilization.
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 PLA, as a kind of Green Polymer Material, because it has biological source, therefore is opened energetically
Exhibition PLA industry can mitigate the pressure to fossil resources, and it also has benifit for alleviating greenhouse effects.But poly- breast
Sour material character is more crisp, and toughness is not enough, therefore it is to improve the important directions of PLA performance that toughness reinforcing is carried out to PLA.Wherein,
It is the common method of plasticizing polylactic acid using PLA and the blending of other polyester polymers.Generally, it is blended into PLA
Other polyester components, can improve the mechanical property of PLA, while remain in that the degradability of PLA, such as PLA/
Polycaprolactone system, PLA/aliphatic-aromatic copolyester, polylactic acid/aliphatic polyester, PLA/poly-hydroxy fatty acid
Deng.
Wherein, aliphatic-aromatic copolyester is a kind of potential polyester material, with good mechanical property,
It can be degraded by compost, part material has biological source, for mitigating fossil resources pressure, mitigate greenhouse effects
It is all beneficial.It is incorporated into PLA in the way of blending, the property of PLA, such as BASF can be effectively improved
Company is by that by ecoflex and polylactic acid blend, can obtain the good product of performanceBut PLA and fat
The compatibility of race-aromatic copolyester is simultaneously bad, and the product of simple blend can show respective glass transition temperature on DSC
Degree, therefore the blending of the two can not reach preferable effect, it usually needs compatilizer is added to improve blending situation.
The content of the invention
The problem of it is an object of the invention to overcome existing PLA and other polyester blend poor compatibilities, there is provided one kind
Poly (lactic acid) composition with excellent compatibility and preparation method thereof.
Generally, PLA copolyesters is prepared using lactide polymerization, be required for additionally add lactide open loop gather
Catalyst needed for closing, the compound such as containing metallic zinc or tin class transition metal, so that obtained PLA is total to
The metallic element of higher amount is remained in polyester, has large effect to the safety in utilization of its product.However, the invention of the present invention
People has found, if using the end of the present invention to trigger lactide and copolymerized therewith for the aliphatic-aromatic copolymer of hydroxyl,
, can drawing in rare earth-Titanium series catalyst of less consumption in the case of terminal hydroxyl using aliphatic-aromatic copolymer
Give, obtain a kind of copolymer-modified poly-lactic acid products of aliphatic-aromatic, i.e. aliphatic-aromatic-PLA copolyesters
Product.It is that can obtain the polydactyl acid product of less tenor using rare earth-Titanium series catalyst of less consumption, and more
Inventor is made it was unexpected that this aliphatic-aromatic-PLA copolyesters product also has extraordinary pliability, as general
Poly (lactic acid) composition obtained by such aliphatic-aromatic-PLA copolyesters product and PLA progress blending extrusion was both
With good compatibility, the fragility defect of PLA script can be overcome again.So as to complete the present invention.
Thus, the present invention provides a kind of poly (lactic acid) composition, and said composition contains PLA and aliphatic-aromatic-poly-
Lactic acid copolyesters product, wherein, metal element content is 0.02 weight in the aliphatic-aromatic-PLA copolyesters product
Measure below %；Also, the preparation method of the aliphatic-aromatic-PLA copolyesters product comprises the following steps：
(1) in the presence of Titanium series catalyst, component a, component b and component c are subjected to esterification；
(2) under vacuum, the esterification reaction mixture of gained in step (1) is subjected to pre-polymerization；
(3) in the presence of rare-earth metal catalyst, the prepolymerization reaction mixture of gained in step (2) is subjected to polycondensation anti-
Should, the product of aliphatic-aromatic copolymer is obtained, wherein, it is described in the product of the aliphatic-aromatic copolymer
The content of Titanium series catalyst is 0.04-0.08 weight %, and the content of the rare-earth metal catalyst is 0.022-0.1 weight %；
(4) product of the aliphatic-aromatic copolymer obtained by step (3) and lactide monomer are subjected to copolyreaction,
Wherein, the product of the aliphatic-aromatic copolymer and the consumption of lactide monomer cause：With the gross weight of lactide monomer
On the basis of, the content of the Titanium series catalyst is 0.017-0.08 weight %, and the content of the rare-earth metal catalyst is
0.0033-0.1 weight %；
Wherein, the component a is C8-C20Aromatic acid, the C8-C20Aromatic acid acid anhydrides and institute
State C8-C20Aromatic acid ester in one or more；The component b is C2-C10Aliphatic dihydroxy alcohol and/or
C3-C10Cycloaliphatic diols；The component c is C2-C20Aliphatic dibasic acid, C3-C10Cycloaliphatic diacid and they
Acid anhydrides in one or more.
Present invention also offers the preparation method of above-mentioned poly (lactic acid) composition, this method includes：
(1) in the presence of Titanium series catalyst, component a, component b and component c are subjected to esterification；
(2) under vacuum, the esterification reaction mixture of gained in step (1) is subjected to pre-polymerization；
(3) in the presence of rare-earth metal catalyst, the prepolymerization reaction mixture of gained in step (2) is subjected to polycondensation anti-
Should, the product of aliphatic-aromatic copolymer is obtained, wherein, it is described in the product of the aliphatic-aromatic copolymer
The content of Titanium series catalyst is 0.04-0.08 weight %, and the content of the rare-earth metal catalyst is 0.022-0.1 weight %；
(4) product of the aliphatic-aromatic copolymer obtained by step (3) and lactide monomer are subjected to copolyreaction,
Wherein, the product of the aliphatic-aromatic copolymer and the consumption of lactide monomer cause：With the gross weight of lactide monomer
On the basis of, the content of the Titanium series catalyst is 0.017-0.08 weight %, and the content of the rare-earth metal catalyst is
0.0033-0.1 weight %；Metallic element contains in aliphatic-aromatic-PLA copolyesters product obtained by the copolyreaction
Measure as below 0.02 weight %；
(5) aliphatic-aromatic-PLA copolyesters product obtained by PLA and step (4) is subjected to blending extrusion,
Wherein, the component a is C8-C20Aromatic acid, the C8-C20Aromatic acid acid anhydrides and institute
State C8-C20Aromatic acid ester in one or more；The component b is C2-C10Aliphatic dihydroxy alcohol and/or
C3-C10Cycloaliphatic diols；The component c is C2-C20Aliphatic dibasic acid, C3-C10Cycloaliphatic diacid and they
Acid anhydrides in one or more.
The poly (lactic acid) composition that the present invention is provided, actually a kind of PLA of blending and modifying, which employs step
(1) aliphatic-aromatic-PLA copolyesters product obtained by-(4), and it is blended with common PLA, by
There is preferable pliability in the aliphatic-aromatic-PLA copolyesters product, can be compatible well with PLA,
And the transparency and degradation property of PLA are kept, simultaneously because the aliphatic-aromatic-PLA copolyesters product has
Relatively low metal element content so that poly (lactic acid) composition of the present invention has higher safety in utilization.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of poly (lactic acid) composition, and said composition contains PLA and aliphatic-aromatic-PLA is common
Polyester product, wherein, in the aliphatic-aromatic-PLA copolyesters product metal element content be 0.02 weight % with
Under；Also, the preparation method of the aliphatic-aromatic-PLA copolyesters product comprises the following steps：
(1) in the presence of Titanium series catalyst, component a, component b and component c are subjected to esterification；
(2) under vacuum, the esterification reaction mixture of gained in step (1) is subjected to pre-polymerization；
(3) in the presence of rare-earth metal catalyst, the prepolymerization reaction mixture of gained in step (2) is subjected to polycondensation anti-
Should, the product of aliphatic-aromatic copolymer is obtained, wherein, it is described in the product of the aliphatic-aromatic copolymer
The content of Titanium series catalyst is 0.04-0.08 weight %, and the content of the rare-earth metal catalyst is 0.022-0.1 weight %；
(4) product of the aliphatic-aromatic copolymer obtained by step (3) and lactide monomer are subjected to copolyreaction,
Wherein, the product of the aliphatic-aromatic copolymer and the consumption of lactide monomer cause：With the gross weight of lactide monomer
On the basis of, the content of the Titanium series catalyst is 0.017-0.08 weight %, and the content of the rare-earth metal catalyst is
0.0033-0.1 weight %；
Wherein, the component a is C8-C20Aromatic acid, the C8-C20Aromatic acid acid anhydrides and institute
State C8-C20Aromatic acid ester in one or more；The component b is C2-C10Aliphatic dihydroxy alcohol and/or
C3-C10Cycloaliphatic diols；The component c is C2-C20Aliphatic dibasic acid, C3-C10Cycloaliphatic diacid and they
Acid anhydrides in one or more.
According to the present invention, the PLA is not particularly limited, can be various PLAs commonly used in the art,
But in order to preferably compatible with the aliphatic-aromatic obtained by the present invention-PLA copolyesters product, under preferable case, institute
The weight average molecular weight that stating PLA has is 8-20 ten thousand, for example, can be 4032 trades mark, the Hai Zheng companies of natureworks companies
The REVODE210 trades mark etc..
It is common to the PLA and aliphatic-aromatic-PLA in the poly (lactic acid) composition according to the present invention
The consumption of polyester product is not particularly limited, as long as enabling to PLA and aliphatic-aromatic-PLA copolyesters
Product has more preferable compatibility, and gained poly (lactic acid) composition is functional, under preferable case, the PLA and fat
The weight ratio of fat race-aromatic series-PLA copolyesters product is 100：10-100, more preferably 100：15-60, it is further excellent
Elect 100 as：25-50.
, according to the invention it is preferred in the case of, on the basis of the gross weight of the poly (lactic acid) composition, the PLA contains
Measure as 50-92 weight %, the content of the aliphatic-aromatic-PLA copolyesters product is 8-50 weight %.More preferably
Ground, on the basis of the gross weight of the poly (lactic acid) composition, the content of the PLA is 65-87 weight %, the aliphatic-
The content of aromatic series-PLA copolyesters product is 13-35 weight %.
According to the present invention, the aliphatic-aromatic-PLA copolyesters product is made by step (1)-(4).Its
In, the product of obtained aliphatic-aromatic copolymer is contained substantial amounts of aliphatic-aromatic by step (1)-(3) in the product
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 being aliphatic-fragrance
The product of race's copolymer is made up of aliphatic-aromatic copolymer and catalyst.Under preferable case, in the product, the titanium
The content of series catalysts is preferably 0.04-0.073 weight %, more preferably 0.05-0.073 weight %.Preferably, the rare earth
The content of metallic catalyst is 0.025-0.095 weight %, more preferably 0.028-0.055 weight %.
, according to the invention it is preferred in the case of, the consumption of the Titanium series catalyst in step (1) and the polycondensation reaction of step (3)
In rare-earth metal catalyst consumption mol ratio be 1：0.4-1, more preferably 1：05-1.
Wherein, the construction unit of the 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 1-20 integer；N is preferably the whole of 1-16
Number；T is preferably 1-20 integer；X can be 1-100 integer, preferably 15-60 integer；Y can be 1-100 integer,
Preferably 15-60 integer.
Under preferable case, Ar is following aryl：
Wherein, R1、R2、R3、R4、R5And R6It is each independently hydrogen, C1-C4 alkyl, F, Cl ,-NO2,-CN or-OR7, its
In, R7For C1-C4 alkyl.
In the case of most preferably, Ar isWherein, R1And R2It is same as above.
According to the present invention, in order to obtain under the preferably transparency and flexility, preferable case, the aliphatic-fragrance
The weight average molecular weight of race's copolymer is 3000-40000, and molecular weight distribution index is 1.2-2.5.It is highly preferred that the aliphatic-
The weight average molecular weight of aromatic copolymer is 6000-35000, and 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,
It is M-phthalic acid, terephthalic acid (TPA), phthalic acid, NDA, 1,5- naphthalenes in the component a under preferable case
One or more in dioctyl phthalate, 2,7- naphthalenedicarboxylic acids, 4,4 '-biphenyl dicarboxylic acid and 3,4 '-biphenyl dicarboxylic acid, more preferably pair
One or more in phthalic acid, M-phthalic acid and phthalic acid, are still more preferably terephthalic acid (TPA).
Under preferable case, the component b be selected from ethylene glycol, diethylene glycol (DEG), propane diols, butanediol, pentanediol, hexylene glycol,
In one or more in cyclohexane diol and norbornane dimethanol, more preferably butanediol, hexylene glycol and cyclohexane diol
One or more, be still more preferably butanediol.
Under preferable case, the component c be succinic acid, succinic anhydride, adipic acid, adipic anhydride, azelaic acid, decanedioic acid,
One or more in dodecanedioic acid, Isosorbide-5-Nitrae-cyclohexane diacid, 1,2,4,5- hexamethylene tetracarboxylic dianhydrides and norbornane diacid,
One or more more preferably in succinic acid, adipic acid and Isosorbide-5-Nitrae-cyclohexane diacid, are still more preferably adipic acid.
According to the present invention, although component a, component b and component the c reaction for carrying out step (1)-(3) can be obtained into described
The product of aliphatic-aromatic copolymer, in order that component a, component b and component c reaction it is more abundant and obtain have give birth to
Under the excellent aliphatic-aromatic copolymer of thing degradation property, preferable case, the component a, component b and component c mol ratio
For 1：(2-5)：(0.8-3), more preferably 1：(2-4.5)：(0.8-2.5), is still more preferably 1：(2-4.4)：(1-
1.5)。
According to the present invention, the consumption of the Titanium series catalyst is not particularly limited, as long as being capable of catalytic step (1)
In the esterification progress, and promote aliphatic-aromatic copolymer and lactide monomer copolymerization, but in order to
There are enough amounts to meet the progress of the esterification, and promotion aliphatic-aromatic copolymer and lactide monomer copolymerization,
It will not give aliphatic-aromatic copolymer the PLA copolymer-modified with the aliphatic-aromatic of lactide monomer copolymerization again
Introduced in product under excessive metal element content, preferable case, using the component a, component b and component c integral molar quantity as
In benchmark, step (1), the consumption of the Titanium series catalyst is 0.01-0.04mol%, more preferably 0.016-0.029mol%.
According to the present invention, similarly, in order to there are enough amounts to meet the progress of polycondensation reaction described in step (3), and promote
Enter aliphatic-aromatic copolymer and lactide monomer copolymerization, aliphatic-aromatic copolymer and lactide monomer will not be given again
Introduced in the copolymer-modified poly-lactic acid products of the aliphatic-aromatic of copolymerization under excessive metal element content, preferable case,
On the basis of the component a, component b and component c integral molar quantity, the consumption of the rare-earth metal catalyst is 0.005-
0.03mol%, more preferably 0.008-0.015mol%.
, according to the invention it is preferred in the case of, the Titanium series catalyst be butyl titanate titanium isopropoxide, titanium dioxide and
One or more in one or more in titanium tetrachloride, more preferably butyl titanate, titanium dioxide and titanium isopropoxide.
The Titanium series catalyst can be commercially available product, can also be made by conventional method, its preparation method will not be repeated here.
, according to the invention it is preferred in the case of, the rare-earth metal catalyst is lanthanum acetylacetone, lanthanum chloride, isopropoxy
One or more in neodymium, 2,6- dibutyl -4- methylenedioxy phenoxies neodymium and Lanthanum Stearate, more preferably lanthanum acetylacetone, isopropyl oxygen
One or more in base neodymium and Lanthanum Stearate.The rare-earth metal catalyst can be commercially available product, can also pass through conventional side
Method be made, for example by document " Inorganic Chemistry 1970,9,2505,
J.Chem.Soc.Chem.Commun.1983, the method described in 1499 " is made, the detailed process of its preparation method, herein not
Repeat again.
, according to the invention it is preferred in the case of, the condition of the esterification includes：Reaction temperature is 150-230 DEG C, reaction
Time is 2-7h.In the case of more preferably, the esterification in step (1) includes：Component a and component b first is carried out into first to be esterified
Reaction, then the material after the first esterification and component c are subjected to the second esterification.Wherein, first esterification
Condition includes：Reaction temperature is 150-230 DEG C, and the reaction time is 1-3h.The condition of second esterification includes：Reaction temperature
Spend for 180-220 DEG C, the reaction time is 1-4h.It is highly preferred that the condition of first esterification includes：Reaction temperature is
180-200 DEG C, the reaction time is 2-3h.The condition of second esterification includes：Reaction temperature is 200-220 DEG C, reaction
Time is 2-4h.
, according to the invention it is preferred in the case of, in step (2), the condition of the pre-polymerization includes：Absolute pressure be 500Pa with
Under, reaction temperature is 200-250 DEG C, and the reaction time is 1-6h.More preferably, the condition of the pre-polymerization includes：Absolute pressure is
Below 400Pa, reaction temperature is 200-240 DEG C, and the reaction time is 1-3h.
Under preferable case, in step (3), the condition of the polycondensation reaction includes：Below 400Pa under absolute pressure, reaction
Temperature is 220-250 DEG C, and the reaction time is 1-5h.It is highly preferred that the condition of the polycondensation reaction includes：Absolute pressure is
Below 400Pa, reaction temperature is 220-240 DEG C, and the reaction time is 1-2h.
, according to the invention it is preferred in the case of, the reaction of above-mentioned steps (1)-(3) is all carried out under nitrogen protection.
According to the present invention, vacuum volatilization drying will be carried out by above-mentioned steps (1)-product made from (3), and remove unreacted
Monomer etc., so as to obtain the product of the aliphatic-aromatic copolymer in the present invention, therefore, the fat in the present invention
The most catalyst added in step (1)-(3) course of reaction, i.e. titanium are remained with the product of race-aromatic copolymer
Series catalysts and rare-earth metal catalyst, and Titanium series catalyst and rare earth are removed in the product of the aliphatic-aromatic copolymer
Nearly all it is the aliphatic-aromatic copolymer outside metallic catalyst.As described above, it will be appreciated by those skilled in the art that
For the aliphatic-aromatic copolymer of the present invention product be by Titanium series catalyst and rare-earth metal catalyst and aliphatic-
Aromatic copolymer is constituted.
According to the present invention, by the product of above-mentioned steps (1)-aliphatic-aromatic copolymer made from (3) in step (4)
In carry out copolyreaction with lactide monomer, so as to obtain the aliphatic-aromatic-PLA copolyesters production of the present invention
Product.
Wherein, because the product of aliphatic-aromatic copolymer comes with a small amount of Titanium series catalyst and rare earth metal is urged
Agent, so that Titanium series catalyst and rare-earth metal catalyst of the copolyreaction of step (4) actually in the part are deposited
Carried out lower, under preferable case, the product of the aliphatic-aromatic copolymer and the consumption of lactide monomer cause：With third
On the basis of the gross weight of lactide monomers, the content of the Titanium series catalyst is 0.02-0.073 weight %, and the rare earth metal is urged
The content of agent is 0.01-0.095 weight %.
In addition, the aliphatic-aromatic copolymer product and the lactide monomer consumption within the above range
The purpose of the present invention can be achieved.It is further preferred that on the basis of the lactide monomer of 100 parts by weight, the fat
The consumption of the product of race-aromatic copolymer is 15-110 parts by weight, more preferably 17-100 parts by weight, still more preferably for
35-100 parts by weight.
, according to the invention it is preferred in the case of, in step (4), the condition of the copolyreaction includes：Reaction temperature is 150-
190 DEG C, the reaction time is 2-5h.It is highly preferred that the condition of the copolyreaction includes：Reaction temperature is 170-185 DEG C, reaction
Time is 2.5-5h.
Wherein, under preferable case, the copolyreaction is carried out in a nitrogen atmosphere, and is first passed through nitrogen to reaction system
Copolyreaction is just proceeded by after 1-5h.
, according to the invention it is preferred in the case of, after the polymerisation terminates, add retarder thinner and be diluted, then add
Enter methanol to be precipitated, to obtain the precipitation of aliphatic-aromatic-PLA copolyesters product.The retarder thinner can be
One or more in chloroform, dichloromethane, tetrahydrofuran and DMF, preferably chloroform, dichloromethane and
One or more in tetrahydrofuran.
Carried out due to the product of the aliphatic-aromatic copolymer in the present invention in step (4) with lactide monomer
Catalyst is not additionally added in copolyreaction so that contain in the aliphatic-aromatic of gained-PLA copolyesters product
Very small amount of metallic element.For example, the metal element content in the aliphatic-aromatic-PLA copolyesters product is
Below 0.02 weight %, preferably 0.002-0.015 weight %, are still more preferably 0.004-0.008 weight %.
According to the present invention, product and being total to that lactide monomer is carried out of the aliphatic-aromatic copolymer in step (4)
Poly- reaction is a kind of random copolymerization, i.e., between aliphatic-aromatic copolymer therein, aliphatic-aromatic copolymer with
Between lactide monomer, it can polymerize between lactide monomer, and the product that they polymerize can also be gathered again
Close, thus aliphatic-aromatic-PLA copolyesters product obtained by the present invention be also one kind through aliphatic-aromatic copolymerization
The atactic polymer for the PLA that thing is modified.Also, in the case of additionally addition catalyst, the aliphatic of gained-
Aromatic series-PLA copolyesters product has preferable pliability, and metal element content is low.
Present invention also offers the preparation method of above-mentioned poly (lactic acid) composition, this method includes：
(1) in the presence of Titanium series catalyst, component a, component b and component c are subjected to esterification；
(2) under vacuum, the esterification reaction mixture of gained in step (1) is subjected to pre-polymerization；
(3) in the presence of rare-earth metal catalyst, the prepolymerization reaction mixture of gained in step (2) is subjected to polycondensation anti-
Should, the product of aliphatic-aromatic copolymer is obtained, wherein, it is described in the product of the aliphatic-aromatic copolymer
The content of Titanium series catalyst is 0.04-0.08 weight %, and the content of the rare-earth metal catalyst is 0.022-0.1 weight %；
(4) product of the aliphatic-aromatic copolymer obtained by step (3) and lactide monomer are subjected to copolyreaction,
Wherein, the product of the aliphatic-aromatic copolymer and the consumption of lactide monomer cause：With the gross weight of lactide monomer
On the basis of, the content of the Titanium series catalyst is 0.017-0.08 weight %, and the content of the rare-earth metal catalyst is
0.0033-0.1 weight %；Metallic element contains in aliphatic-aromatic-PLA copolyesters product obtained by the copolyreaction
Measure as below 0.02 weight %；
(5) aliphatic-aromatic-PLA copolyesters product obtained by PLA and step (4) is subjected to blending extrusion,
Wherein, the component a is C8-C20Aromatic acid, the C8-C20Aromatic acid acid anhydrides and institute
State C8-C20Aromatic acid ester in one or more；The component b is C2-C10Aliphatic dihydroxy alcohol and/or
C3-C10Cycloaliphatic diols；The component c is C2-C20Aliphatic dibasic acid, C3-C10Cycloaliphatic diacid and they
Acid anhydrides in one or more.
Wherein, step (1)-(4) are similar to foregoing description, are not discussed here.
And the blending extrusion of step (5) can using the conventional blending extrusion in this area method, the present invention to this not
There is any restriction.
By the preparation method of the poly (lactic acid) composition of the present invention, a kind of PLA being modified by blending method will be obtained
Product, be the present invention poly (lactic acid) composition.It is good that the poly (lactic acid) composition can both keep that PLA has
Biological degradation rate, hypotoxicity, can obtain higher pliability again.
The present invention will be described in detail by way of examples below.
In following catalyst preparation example, preparation example, preparation comparative example, embodiment and comparative example,
In its aliphatic-aromatic-PLA copolyesters, polylactic acid chain segment/copolyesters weight ratio is by nuclear magnetic resonance
What method was measured；
Weight average molecular weight and molecular weight distributing index are determined using gel permeation chromatography (GPC), wherein, with tetrahydrochysene
Furans (THF) is solvent, on Waters-208 (the band RI detectors of Waters 2410,1.5mL/min flow velocitys, 30 DEG C) instrument
Measurement, molecular weight is calibrated with the linear polystyrene standards of single dispersing；
Tensile strength and fracture tensile strength are that the method according to described in GB/T 1040.2-2006 is measured；
Biodegradability is that the method according to described in GB/T 19275-2003 is detected, mainly will test
Mass loss of the post-consumer polymer sample relative to the polymer samples before test accounts for the percentage by weight of test prepolymer sample
To represent biological degradation rate；
The toxicity of biodegradable product is that the method according to described in DIN 38412-30-1989 is detected.
Catalyst preparation example 1
Lanthanum chloride 9.37mmol is dissolved in 50mL water, the aqueous solution of the acetylacetone,2,4-pentanedione containing 56.2mmol is then added to
In, it is stirred at room temperature, pH is adjusted to neutrality by adding the 2N KOH aqueous solution.Reactant mixture is stirred, filtering, in vacuum
Dried at 60 DEG C, obtain lanthanum acetylacetone 4g.
Catalyst preparation example 2
Lanthanum chloride 9.37mmol is dissolved in 50mL water, the aqueous solution of the odium stearate containing 20mmol is then added to
In, it is stirred at room temperature, pH is adjusted to neutrality by adding the 2N HCl aqueous solution.Reactant mixture is stirred, filtering, in vacuum
Dried at 60 DEG C, obtain Lanthanum Stearate 11g.
Preparation example 1
2.2mol terephthalic acid (TPA)s, 5mol butanediols and 1.6mmol butyl titanates is (public purchased from Beijing chemical reagent
Department, chemistry is pure) it is added in reactor, and under nitrogen protection, backflow is heated with stirring to, reaction temperature is controlled at 180 DEG C, and
The water steamed is collected, treats that water is almost collected and finishes and (about react 2h).2.5mol succinic acid is it is possible to additionally incorporate into system, continues to stir
Backflow is heated to, reaction temperature is controlled at 200 DEG C, is collected the water steamed, is almost collected to water and finish and (about react 2h).Then,
By the system temperature be 230 DEG C, absolute pressure be pre-polymerization about 1h under conditions of 400Pa.Finally, added into the system
0.85mmol lanthanum acetylacetones, are 230 DEG C, under conditions of absolute pressure is maintained at below 200Pa in temperature, polycondensation about 1h leads to
The white aliphatic-aromatic copolyester P1 that vacuum volatilization is dried to obtain 750g is crossed, its weight average molecular weight is 10000, molecule
Measure during profile exponent is 2.2, and copolyesters P1, the content of butyl titanate is 0.060 weight %, lanthanum acetylacetone contains
Measure as 0.041 weight %.
80g L- lactide monomers (LLA) and 30g aliphatic-aromatic copolyesters P1 is added separately in reactor (fat
On the basis of the total amount of fat race-aromatic copolymer P1 and lactide monomer, the content of butyl titanate is 0.016 weight %, second
The content of acyl acetone lanthanum is 0.011 weight %), 5h will be purged with high pure nitrogen after being well mixed, under nitrogen atmosphere will reaction
Bottle, which is placed at 170 DEG C, to be reacted after 5h, and cooling with chloroform diluted mixture, and is precipitated in absolute methanol, gained precipitation
Thing be aliphatic-aromatic-PLA copolyesters product A1 (97g, wherein, the content of titanium is 0.0022 weight %, and lanthanum contains
Measure as 0.0036 weight %), its copolyesters/lactide weight ratio, weight average molecular weight, molecular weight distributing index, tensile strength and
It is broken elongation rate as shown in table 1.
Preparation example 2
2.2mol terephthalic acid (TPA)s, 5mol butanediols and 1.6mmol butyl titanates are added in reactor, and in nitrogen
Under gas shielded, backflow is heated with stirring to, reaction temperature is controlled at 200 DEG C, and collects the water steamed, treated that water is almost collected and finish
(about reacting 2h).2.5mol succinic acid is it is possible to additionally incorporate into system, continues to be heated with stirring to backflow, reaction temperature is controlled 220
DEG C, the water steamed is collected, is almost collected to water and is finished and (about react 2h).Then, it is 240 DEG C, absolute pressure in temperature by the system
Power is pre-polymerization about 1h under conditions of 400Pa.Finally, into the system add 0.85mmol Lanthanum Stearates, temperature be 240 DEG C,
Absolute pressure is maintained under conditions of below 200Pa, and polycondensation about 1.5h, the purification process dried by vacuum volatilization obtains 700g
White aliphatic-aromatic copolyester P2, its weight average molecular weight be 31000, molecular weight distributing index is 1.67, and should
In copolyesters P2, the content of butyl titanate is 0.041 weight %, and the content of Lanthanum Stearate is 0.025 weight %.
80g L- lactide monomers (LLA) and 30g aliphatic-aromatic copolyesters P2 is added separately in reactor (fat
On the basis of the total amount of fat race-aromatic copolymer P2 and lactide monomer, the content of butyl titanate is 0.011 weight %, firmly
The content of resin acid lanthanum is 0.0068 weight %), 5h will be purged with high pure nitrogen after being well mixed, under nitrogen atmosphere by reaction bulb
It is placed at 170 DEG C and reacts after 5h, cooling with chloroform diluted mixture, and is precipitated, gained sediment in absolute methanol
As aliphatic-aromatic-PLA copolyesters product A2 (95g, wherein, the content of titanium is 0.0016 weight %, the content of lanthanum
For 0.0025 weight %), its copolyesters/lactide weight ratio, weight average molecular weight, molecular weight distributing index, tensile strength and disconnected
Split elongation rate as shown in table 1.
Prepare comparative example 1
Using the method described in preparation example 1, except that, it is common in L- lactide monomers (LLA) and aliphatic-aromatic
Polyester P1 reactions take a step forward the stannous octoate for adding 82mg as catalyst, and gained sediment is aliphatic-aromatic-poly-
Lactic acid copolyesters product DA1 (106g, wherein, the content of titanium is 0.0015 weight %, and the content of lanthanum is 0.003 weight %, tin
Content be 0.02 weight %), its copolyesters/lactide weight ratio, weight average molecular weight, molecular weight distributing index, tensile strength and
It is broken elongation rate as shown in table 1.
Table 1
Embodiment 1-3
The present embodiment is used for the poly (lactic acid) composition for illustrating the present invention.
By 200g PLAs (nature works company trade mark 4042D) respectively with 100g, 50g and 120g aliphatic-
Aromatic series-PLA copolyesters product A1 is added in double screw extruder, is uniformly mixed and is extruded, wherein, from charging aperture to
Each section of temperature of extrusion is followed successively by 100 DEG C, 170 DEG C, 170 DEG C, 160 DEG C.Extrude obtained poly (lactic acid) composition and carry out biological drop
Solution rate, the toxicity of catabolite are measured, and progress tensile strength and fracture drawing after 15 × 15 × 2mm sample panel is made
The measure of rate is stretched, it the results are shown in Table 2.
Embodiment 4-5
The present embodiment is used for the poly (lactic acid) composition for illustrating the present invention.
By the aliphatic-fragrance of 200g PLAs (nature works company trade mark 4042D) respectively with 100g and 120g
Race-PLA copolyesters product A2 is added in double screw extruder, is uniformly mixed and is extruded, wherein, from charging aperture to extrusion
Each section of temperature of mouth is followed successively by 100 DEG C, 170 DEG C, 170 DEG C, 160 DEG C.Extrude obtained poly (lactic acid) composition carry out biological degradation rate,
The toxicity of catabolite is measured, and tensile strength and the break-draw rate of carrying out is made after 15 × 15 × 2mm sample panel
Measure, it the results are shown in Table 2.
Embodiment 6
Method according to embodiment 1, except that, aliphatic-aromatic-PLA copolyesters product A1 use
Measure as 35g, the poly (lactic acid) composition that extrusion is obtained carries out biological degradation rate, the toxicity of catabolite and is measured, and is made
The measure of tensile strength and break-draw rate is carried out after 15 × 15 × 2mm sample panel, it the results are shown in Table 2.
Embodiment 7
Method according to embodiment 1, except that, aliphatic-aromatic-PLA copolyesters product A1 use
Measure as 180g, the poly (lactic acid) composition that extrusion is obtained carries out biological degradation rate, the toxicity of catabolite and is measured, and is made
The measure of tensile strength and break-draw rate is carried out after 15 × 15 × 2mm sample panel, it the results are shown in Table 2.
Comparative example 1
Method according to embodiment 1, except that, replaced using 100g aliphatic-aromatic copolyester P1
Aliphatic-aromatic-PLA copolyesters product A1, extrudes obtained poly (lactic acid) composition and carries out biological degradation rate, degraded production
The toxicity test of thing, and the measure that tensile strength and break-draw rate are carried out after 15 × 15 × 2mm sample panel is made, it is tied
Fruit is shown in Table 2.
Comparative example 2
Method according to embodiment 4, except that, replaced using 100g aliphatic-aromatic copolyester P2
Aliphatic-aromatic-PLA copolyesters product A2, extrudes obtained poly (lactic acid) composition and carries out biological degradation rate, degraded production
The toxicity test of thing, and the measure that tensile strength and break-draw rate are carried out after 15 × 15 × 2mm sample panel is made, it is tied
Fruit is shown in Table 2.
Comparative example 3
Method according to embodiment 1, except that, using 100g aliphatic-aromatic-PLA copolyesters
Product DA1 replaces A1, extrudes obtained poly (lactic acid) composition and carries out biological degradation rate, the toxicity test of catabolite, and system
The measure of tensile strength and break-draw rate is carried out after into 15 × 15 × 2mm sample panel, it the results are shown in Table 2.
Table 2
| Copolyesters | Tensile strength (MPa) | Elongation at break (%) | Biological degradation rate | The toxicity of catabolite |
| Embodiment 1 | 25.6 | 51 | 100% | It is nontoxic |
| Embodiment 2 | 30 | 26 | 100% | It is nontoxic |
| Embodiment 3 | 21.3 | 120 | 100% | It is nontoxic |
| Embodiment 4 | 29.5 | 44 | 100% | It is nontoxic |
| Embodiment 5 | 22 | 84 | 100% | It is nontoxic |
| Embodiment 6 | 35.2 | 25 | 100% | It is nontoxic |
| Embodiment 7 | 22.7 | 80 | 100% | It is nontoxic |
| Comparative example 1 | 26.9 | 18 | 100% | It is nontoxic |
| Comparative example 2 | 35 | 15 | 100% | It is nontoxic |
| Comparative example 3 | 16.5 | 13 | 100% | It is nontoxic |
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (44)
1. a kind of poly (lactic acid) composition, it is characterised in that said composition contains PLA and aliphatic-aromatic-PLA is common
Polyester product, wherein, in the aliphatic-aromatic-PLA copolyesters product metal element content be 0.02 weight % with
Under；Also, the preparation method of the aliphatic-aromatic-PLA copolyesters product comprises the following steps：
(1) in the presence of Titanium series catalyst, component a, component b and component c are subjected to esterification；
(2) under vacuum, the esterification reaction mixture of gained in step (1) is subjected to pre-polymerization；
(3) in the presence of rare-earth metal catalyst, the prepolymerization reaction mixture of gained in step (2) is subjected to polycondensation reaction,
The product of aliphatic-aromatic copolymer is obtained, wherein, in the product of the aliphatic-aromatic copolymer, the titanium system
The content of catalyst is 0.04-0.08 weight %, and the content of the rare-earth metal catalyst is 0.022-0.1 weight %；
(4) product of the aliphatic-aromatic copolymer obtained by step (3) and lactide monomer are subjected to copolyreaction, wherein,
The product of the aliphatic-aromatic copolymer and the consumption of lactide monomer cause：Using the gross weight of lactide monomer as base
Standard, the content of the Titanium series catalyst is 0.017-0.08 weight %, and the content of the rare-earth metal catalyst is 0.0033-
0.1 weight %；
Wherein, the component a is C8-C20Aromatic acid, the C8-C20Aromatic acid acid anhydrides and the C8-
C20Aromatic acid ester in one or more；The component b is C2-C10Aliphatic dihydroxy alcohol and/or C3-C10's
Cycloaliphatic diols；The component c is C2-C20Aliphatic dibasic acid and its acid anhydrides, 1,4- cyclohexane diacids, 1,2,4,5- rings
One or more in hexane tetracarboxylic dianhydride and norbornane diacid.
2. composition according to claim 1, wherein, the PLA and aliphatic-aromatic-PLA copolyesters production
The weight ratio of product is 100：10-100.
3. composition according to claim 2, wherein, the PLA and aliphatic-aromatic-PLA copolyesters production
The weight ratio of product is 100：15-60.
4. composition according to claim 3, wherein, the PLA and aliphatic-aromatic-PLA copolyesters production
The weight ratio of product is 100：25-50.
5. the composition according to any one in claim 1-4, wherein, using the gross weight of the poly (lactic acid) composition as
Benchmark, the content of the PLA is 50-92 weight %, and the content of the aliphatic-aromatic-PLA copolyesters product is
8-50 weight %.
6. composition according to claim 1, wherein, in step (4), the product of the aliphatic-aromatic copolymer
Cause with the consumption of lactide monomer：On the basis of the gross weight of lactide monomer, the content of the Titanium series catalyst is 0.02-
0.073 weight %, the content of the rare-earth metal catalyst is 0.01-0.095 weight %.
7. composition according to claim 1, wherein, the consumption of the Titanium series catalyst in step (1) and the contracting of step (3)
The mol ratio of the consumption of rare-earth metal catalyst in poly- reaction is 1：0.4-1.
8. composition according to claim 1, wherein, the Titanium series catalyst is butyl titanate, titanium isopropoxide, two
One or more in titanium oxide and titanium tetrachloride；The rare-earth metal catalyst is lanthanum acetylacetone, lanthanum chloride, isopropoxy
One or more in neodymium, 2,6- dibutyl -4- methylenedioxy phenoxies neodymium and Lanthanum Stearate.
9. composition according to claim 1, wherein, the component a is M-phthalic acid, terephthalic acid (TPA), adjacent benzene two
Formic acid, 2,6- naphthalenedicarboxylic acids, 1,5- naphthalenedicarboxylic acids, 2,7- naphthalenedicarboxylic acids, 4,4 '-biphenyl dicarboxylic acid and 3,4 '-biphenyl dicarboxylic acid
In one or more；The component b is selected from ethylene glycol, diethylene glycol (DEG), propane diols, butanediol, pentanediol, hexylene glycol, hexamethylene
One or more in alkane glycol and norbornane dimethanol；The component c is succinic acid, succinic anhydride, adipic acid, adipic acid
Acid anhydride, azelaic acid, decanedioic acid, dodecanedioic acid, 1,4- cyclohexane diacids, 1,2,4,5- hexamethylenes tetracarboxylic dianhydride and norbornane two
One or more in acid.
10. composition according to claim 9, wherein, the component a is terephthalic acid (TPA), M-phthalic acid and adjacent benzene
One or more in dioctyl phthalate.
11. composition according to claim 9, wherein, the component b is in butanediol, hexylene glycol and cyclohexane diol
One or more.
12. composition according to claim 9, wherein, the component c is succinic acid, adipic acid and Isosorbide-5-Nitrae-hexamethylene two
One or more in acid.
13. composition according to claim 1, wherein, the component a, component b and component c mol ratio are 1：(2-
5)：(0.8-3).
14. composition according to claim 13, wherein, the component a, component b and component c mol ratio are 1：(2-
4.5)：(0.8-2.5).
15. composition according to claim 1, wherein, the integral molar quantity using the component a, component b and component c is base
In standard, step (1), the consumption of the Titanium series catalyst is 0.01-0.04mol%.
16. composition according to claim 15, wherein, the integral molar quantity using the component a, component b and component c is base
In standard, step (1), the consumption of the Titanium series catalyst is 0.016-0.029mol%.
17. composition according to claim 1, wherein, the integral molar quantity using the component a, component b and component c is base
In standard, step (3), the consumption of the rare-earth metal catalyst is 0.005-0.03mol%.
18. composition according to claim 17, wherein, the integral molar quantity using the component a, component b and component c is base
In standard, step (3), the consumption of the rare-earth metal catalyst is 0.008-0.015mol%.
19. composition according to claim 1, wherein, the Weight-average molecular of the product of the aliphatic-aromatic copolymer
Measure as 3000-40000, molecular weight distribution index is 1.2-2.5.
20. composition according to claim 1, wherein, in step (1), the condition of the esterification includes：Reaction temperature
Spend for 150-230 DEG C, the reaction time is 2-7h；In step (2), the condition of the pre-polymerization includes：Absolute pressure be 500Pa with
Under, reaction temperature is 200-250 DEG C, and the reaction time is 1-6h；In step (3), the condition of the polycondensation reaction includes：Absolute pressure
Power is below 400Pa, and reaction temperature is 220-250 DEG C, and the reaction time is 1-5h；In step (4), the condition of the copolyreaction
Including：Reaction temperature is 150-190 DEG C, and the reaction time is 2-5h.
21. composition according to claim 20, wherein, in step (1), the esterification includes：First by component a and
Component b carries out the first esterification, then the material after the first esterification and component c are carried out into the second esterification；Wherein, institute
Stating the condition of the first esterification includes：Reaction temperature is 150-230 DEG C, and the reaction time is 1-3h；Second esterification
Condition include：Reaction temperature is 180-220 DEG C, and the reaction time is 1-4h.
22. composition according to claim 1, wherein, it is golden in the aliphatic-aromatic-PLA copolyesters product
Category constituent content is 0.002-0.015 weight %.
23. the preparation method of the poly (lactic acid) composition described in a kind of claim 1, it is characterised in that this method includes：
(1) in the presence of Titanium series catalyst, component a, component b and component c are subjected to esterification；
(2) under vacuum, the esterification reaction mixture of gained in step (1) is subjected to pre-polymerization；
(3) in the presence of rare-earth metal catalyst, the prepolymerization reaction mixture of gained in step (2) is subjected to polycondensation reaction,
The product of aliphatic-aromatic copolymer is obtained, wherein, in the product of the aliphatic-aromatic copolymer, the titanium system
The content of catalyst is 0.04-0.08 weight %, and the content of the rare-earth metal catalyst is 0.022-0.1 weight %；
(4) product of the aliphatic-aromatic copolymer obtained by step (3) and lactide monomer are subjected to copolyreaction, wherein,
The product of the aliphatic-aromatic copolymer and the consumption of lactide monomer cause：Using the gross weight of lactide monomer as base
Standard, the content of the Titanium series catalyst is 0.017-0.08 weight %, and the content of the rare-earth metal catalyst is 0.0033-
0.1 weight %；Metal element content is in aliphatic-aromatic-PLA copolyesters product obtained by the copolyreaction
Below 0.02 weight %；
(5) aliphatic-aromatic-PLA copolyesters product obtained by PLA and step (4) is subjected to blending extrusion,
Wherein, the component a is C8-C20Aromatic acid, the C8-C20Aromatic acid acid anhydrides and the C8-
C20Aromatic acid ester in one or more；The component b is C2-C10Aliphatic dihydroxy alcohol and/or C3-C10's
Cycloaliphatic diols；The component c is C2-C20Aliphatic dibasic acid and its acid anhydrides, 1,4- cyclohexane diacids, 1,2,4,5- rings
One or more in hexane tetracarboxylic dianhydride and norbornane diacid.
24. method according to claim 23, wherein, the PLA and aliphatic-aromatic-PLA copolyesters production
The weight ratio of product is 100：10-100.
25. method according to claim 24, wherein, the PLA and aliphatic-aromatic-PLA copolyesters production
The weight ratio of product is 100：15-60.
26. method according to claim 25, wherein, the PLA and aliphatic-aromatic-PLA copolyesters production
The weight ratio of product is 100：25-50.
27. the method according to any one in claim 23-26, wherein, with the gross weight of the poly (lactic acid) composition
On the basis of, the content of the PLA is 50-92 weight %, the content of the aliphatic-aromatic-PLA copolyesters product
For 8-50 weight %.
28. method according to claim 23, wherein, in step (4), the product of the aliphatic-aromatic copolymer
Cause with the consumption of lactide monomer：On the basis of the gross weight of lactide monomer, the content of the Titanium series catalyst is 0.02-
0.073 weight %, the content of the rare-earth metal catalyst is 0.01-0.095 weight %.
29. method according to claim 23, wherein, the consumption of the Titanium series catalyst in step (1) and the contracting of step (3)
The mol ratio of the consumption of rare-earth metal catalyst in poly- reaction is 1：0.4-1.
30. method according to claim 23, wherein, the Titanium series catalyst is butyl titanate, titanium isopropoxide, two
One or more in titanium oxide and titanium tetrachloride；The rare-earth metal catalyst is lanthanum acetylacetone, lanthanum chloride, isopropoxy
One or more in neodymium, 2,6- dibutyl -4- methylenedioxy phenoxies neodymium and Lanthanum Stearate.
31. method according to claim 23, wherein, the component a is M-phthalic acid, terephthalic acid (TPA), adjacent benzene two
Formic acid, 2,6- naphthalenedicarboxylic acids, 1,5- naphthalenedicarboxylic acids, 2,7- naphthalenedicarboxylic acids, 4,4 '-biphenyl dicarboxylic acid and 3,4 '-biphenyl dicarboxylic acid
In one or more；The component b is selected from ethylene glycol, diethylene glycol (DEG), propane diols, butanediol, pentanediol, hexylene glycol, hexamethylene
One or more in alkane glycol and norbornane dimethanol；The component c is succinic acid, succinic anhydride, adipic acid, adipic acid
Acid anhydride, azelaic acid, decanedioic acid, dodecanedioic acid, 1,4- cyclohexane diacids, 1,2,4,5- hexamethylenes tetracarboxylic dianhydride and norbornane two
One or more in acid.
32. method according to claim 31, wherein, the component a is terephthalic acid (TPA), M-phthalic acid and adjacent benzene two
One or more in formic acid.
33. method according to claim 31, wherein, the component b is in butanediol, hexylene glycol and cyclohexane diol
It is one or more.
34. method according to claim 31, wherein, the component c is succinic acid, adipic acid and Isosorbide-5-Nitrae-cyclohexane diacid
In one or more.
35. method according to claim 23, wherein, the component a, component b and component c mol ratio are 1：(2-5)：
(0.8-3)。
36. method according to claim 35, wherein, the component a, component b and component c mol ratio are 1：(2-
4.5)：(0.8-2.5).
37. method according to claim 23, wherein, the integral molar quantity using the component a, component b and component c is base
In standard, step (1), the consumption of the Titanium series catalyst is 0.01-0.04mol%.
38. the method according to claim 37, wherein, the integral molar quantity using the component a, component b and component c is base
In standard, step (1), the consumption of the Titanium series catalyst is 0.016-0.029mol%.
39. method according to claim 23, wherein, the integral molar quantity using the component a, component b and component c is base
In standard, step (3), the consumption of the rare-earth metal catalyst is 0.005-0.03mol%.
40. the method according to claim 39, wherein, the integral molar quantity using the component a, component b and component c is base
In standard, step (3), the consumption of the rare-earth metal catalyst is 0.008-0.015mol%.
41. method according to claim 23, wherein, the Weight-average molecular of the product of the aliphatic-aromatic copolymer
Measure as 3000-40000, molecular weight distribution index is 1.2-2.5.
42. method according to claim 23, wherein, in step (1), the condition of the esterification includes：Reaction temperature
Spend for 150-230 DEG C, the reaction time is 2-7h；In step (2), the condition of the pre-polymerization includes：Absolute pressure be 500Pa with
Under, reaction temperature is 200-250 DEG C, and the reaction time is 1-6h；In step (3), the condition of the polycondensation reaction includes：Absolute pressure
Power is below 400Pa, and reaction temperature is 220-250 DEG C, and the reaction time is 1-5h；In step (4), the condition of the copolyreaction
Including：Reaction temperature is 150-190 DEG C, and the reaction time is 2-5h.
43. method according to claim 42, wherein, in step (1), the esterification includes：First by component a and group
Divide b to carry out the first esterification, then the material after the first esterification and component c are subjected to the second esterification；Wherein, it is described
The condition of first esterification includes：Reaction temperature is 150-230 DEG C, and the reaction time is 1-3h；Second esterification
Condition includes：Reaction temperature is 180-220 DEG C, and the reaction time is 1-4h.
44. method according to claim 23, wherein, metal in the aliphatic-aromatic-PLA copolyesters product
Constituent content is 0.002-0.015 weight %.
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| CN109721699B (en) * | 2017-10-31 | 2022-03-29 | 中国石油化工股份有限公司 | Polylactic acid copolyester and preparation method thereof, and biaxially stretched polylactic acid copolyester film and preparation method thereof |
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