CN109721976A - Poly (lactic acid) composition and preparation method thereof and biaxially stretched polylactic acid film and preparation method thereof - Google Patents
Poly (lactic acid) composition and preparation method thereof and biaxially stretched polylactic acid film and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to polylactic acid film fields, and in particular, to poly (lactic acid) composition and preparation method thereof and biaxially stretched polylactic acid film and preparation method thereof.The composition contains polylactic acid and polylactic acid copolyesters, which is the linear copolyester containing aliphatic-aromatic cosegment, polylactic acid chain segment and the chain extender structures provided by chain extender；The aliphatic-aromatic cosegment is made of aromatic polyester structure and aliphatic polyester structure；The aromatic polyester structure is that the polyester construction formed is copolymerized by component a and component b, and the aliphatic polyester structure is to be copolymerized the polyester construction formed by component c and component b.Biaxially stretched polylactic acid film provided by the invention has in the case where guaranteeing higher mechanical property compared with high flexibility, so that proof strength but also noise can be reduced.
Description
Technical field
The present invention relates to polylactic acid film fields, and in particular, to poly (lactic acid) composition and preparation method thereof and two-way drawing
Stretched polylactic acid film and preparation method thereof.
Background technique
Biaxial tension technology can be with processing of polyolefins, nylon, polylactic acid, polyethylene terephthalate, polystyrene
Equal materials, obtained biaxially oriented film surface is smooth, and transparency is high, and mechanical strength is good, is widely used on packaging film
It is general.But the type of current biaxial stretching film is still fewer, it is therefore desirable to develop more biaxial stretching film types, study its property
Can, widen the application type and application category of biaxial stretching film.
Polylactic acid biaxial stretching film is a kind of promising biaxially oriented film.But the biaxially oriented film of polylactic acid
There are one clearly the disadvantage is that noise is very big, this can bring puzzlement in much packaging occasions to consumer.
Summary of the invention
The defect that it is an object of the invention to overcome existing polylactic acid biaxial stretching film noise excessive provides one kind and exists
Guarantee have under higher mechanical property compared with biaxially stretched polylactic acid film of high flexibility and preparation method thereof and polylactic acid group
Close object and preparation method thereof, which proof strength but also can reduce noise.
To achieve the goals above, one aspect of the present invention provides a kind of poly (lactic acid) composition, and the composition contains polylactic acid
With polylactic acid copolyesters, which is containing aliphatic-aromatic cosegment, polylactic acid chain segment and by chain extender
The linear copolyester of the chain extender structures of offer；
Wherein, the aliphatic-aromatic cosegment is made of aromatic polyester structure and aliphatic polyester structure；The virtue
Fragrant polyester construction is that the polyester construction formed is copolymerized by component a and component b, and the aliphatic polyester structure is by component c and component b
It is copolymerized the polyester construction formed；
Wherein, the component a is C8-C20Aromatic acid, the C8-C20Aromatic acid acid anhydrides and institute
State C8-C20One of the ester of aromatic acid or a variety of；The component b is C2-C10Aliphatic dihydroxy alcohol and/or
C3-C10Cycloaliphatic diols；The component c is C2-C20Aliphatic dibasic acid, C5-C10Cycloaliphatic diacid and they
One of acid anhydrides or a variety of；
Wherein, on the basis of the weight of the polylactic acid copolyesters, the content of the aliphatic-aromatic cosegment is
9-90 weight %, the content of the polylactic acid chain segment are 9-90 weight %, and the content of the chain extender structures is 0.1-5 weight
Measure %.
Second aspect of the present invention provides a kind of preparation method of poly (lactic acid) composition, this method comprises:
(1) in the presence of Titanium series catalyst, component a, component b and component c are subjected to esterification；
(2) under vacuum conditions, esterification reaction mixture obtained in step (1) is subjected to pre-polymerization；
(3) in the presence of rare-earth metal catalyst, it is anti-that prepolymerization reaction mixture obtained in step (2) is subjected to polycondensation
It answers, obtains the product of aliphatic-aromatic copolymer；
(4) product of the resulting aliphatic-aromatic copolymer of step (3) and lactide monomer are subjected to copolyreaction；
(5) the resulting copolyreaction product of step (4) and chain extender are subjected to chain extending reaction, obtain polylactic acid copolyesters；
(6) polylactic acid copolyesters obtained by polylactic acid and step (5) is subjected to blending extrusion；
Wherein, the component a is C8-C20Aromatic acid, the C8-C20Aromatic acid acid anhydrides and institute
State C8-C20One of the ester of aromatic acid or a variety of；The component b is C2-C10Aliphatic dihydroxy alcohol and/or
C3-C10Cycloaliphatic diols；The component c is C2-C20Aliphatic dibasic acid, C5-C10Cycloaliphatic diacid and they
One of acid anhydrides or a variety of；
This method make resulting polylactic acid copolyesters be containing aliphatic-aromatic cosegment, polylactic acid chain segment and
By the linear copolyester for the chain extender structures that chain extender provides, and in the polylactic acid copolyesters, the aliphatic-aromatic is total
The content of poly chain section is 9-90 weight %, and the content of the polylactic acid chain segment is 9-90 weight %, and the chain extender structures contain
Amount is 0.1-5 weight %.
Third aspect present invention provides the poly (lactic acid) composition as made from above-mentioned preparation method.
Fourth aspect present invention provides a kind of preparation method of biaxially stretched polylactic acid film, this method comprises:
(1) above-mentioned poly (lactic acid) composition is subjected to melting curtain coating slab, obtains polylactic acid slab；
(2) the polylactic acid slab is subjected to biaxial tension to form a film.
Fifth aspect present invention provides biaxially stretched polylactic acid film prepared by the above method.
Biaxially stretched polylactic acid film provided by the invention, has in the case where guaranteeing higher mechanical property compared with high flexibility, from
And can proof strength can reduce noise.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of poly (lactic acid) composition, and the composition contains polylactic acid and polylactic acid copolyesters, should
Polylactic acid copolyesters is to contain aliphatic-aromatic cosegment, polylactic acid chain segment and the chain extender structures provided by chain extender
Linear copolyester；
Wherein, the aliphatic-aromatic cosegment is made of aromatic polyester structure and aliphatic polyester structure；The virtue
Fragrant polyester construction is that the polyester construction formed is copolymerized by component a and component b, and the aliphatic polyester structure is by component c and component b
It is copolymerized the polyester construction formed；
Wherein, the component a is C8-C20Aromatic acid, the C8-C20Aromatic acid acid anhydrides and institute
State C8-C20One of the ester of aromatic acid or a variety of；The component b is C2-C10Aliphatic dihydroxy alcohol (i.e. C2-
C20Aliphatic linear dihydric alcohol) and/or C3-C10Cycloaliphatic diols；The component c is C2-C20Aliphatic dibasic acid
(i.e. C2-C20Aliphatic linear binary acid), C5-C10Cycloaliphatic diacid and their one of acid anhydrides or a variety of；
Wherein, on the basis of the weight of the polylactic acid copolyesters, the content of the aliphatic-aromatic cosegment is
9-90 weight %, the content of the polylactic acid chain segment are 9-90 weight %, and the content of the chain extender structures is 0.1-5 weight
Measure %.
According to the present invention, the polylactic acid is not particularly limited, can is various polylactic acid commonly used in the art,
However in order to preferably compatible with the resulting polylactic acid copolyesters of the present invention, under preferable case, the weight that the polylactic acid has is equal
Molecular weight is 8-20 ten thousand, such as the REVODE210 trade mark of 4042D, Hai Zheng company that can be natureworks company etc..
According to the present invention, the polylactic acid and the proportion of polylactic acid copolyesters can change in a wider range, preferably feelings
Under condition, the weight ratio of the polylactic acid and polylactic acid copolyesters is 100:10-100, preferably 100:15-60, more preferably
100:25-50.
According to the present invention, polylactic acid copolyesters of the invention is previously formed by aromatic polyester structure and aliphatic polyester structure
The aliphatic-aromatic copolymer of composition, end are essentially hydroxyl, it is believed that are a kind of macromole evocating agents, then introduce
Lactide monomer, so that the both ends of aliphatic-aromatic copolymer obtain polylactic acid-(fat in conjunction with upper polylactic acid chain segment
Race-aromatic copolyester segment)-polylactic acid, end is essentially hydroxyl, then adds chain extender, increases polylactic acid-(rouge
Fat race-aromatic copolyester segment)-polylactic acid molecular weight, form polylactic acid copolyesters of the invention.
According to the present invention, described poly- although the content for controlling the aliphatic-aromatic cosegment is 9-90 weight %
The content of lactic acid segment is 9-90 weight %, and the content of the chain extender structures is 0.1-5 weight %, but in order to obtain
The more excellent polylactic acid copolyesters of performance, it is preferable that on the basis of the weight of the polylactic acid copolyesters, the aliphatic-
The content of aromatic copolyester segment is 12-78.5 weight %, and the content of the polylactic acid chain segment is 22-80 weight %, the expansion
The content of chain agent structure is 0.5-2 weight %.It is highly preferred that on the basis of the weight of the polylactic acid copolyesters, the fat
Race-aromatic copolyester segment content is 25-60 weight %, and the content of the polylactic acid chain segment is 40-70 weight %, the expansion
The content of chain agent structure is 0.5-1.5 weight %.
Wherein, the structural unit of the aliphatic-aromatic cosegment 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 whole of 1-16
Number；T is preferably the integer of 1-20；X can be the integer of 1-100, the preferably integer of 15-60；Y can be the integer of 1-100,
The preferably 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,
In, R7For the alkyl of C1-C4.
In most preferred situation, Ar isWherein, R1And R2It is same as above.
According to the present invention, in order to obtain the preferably transparency and flexility, under preferable case, the aliphatic-fragrance
The weight average molecular weight of race's cosegment is 3,000-40,000g/mol, molecular weight distribution index 1.2-2.5.It is highly preferred that institute
The weight average molecular weight for stating aliphatic-aromatic cosegment is 6,000-35,000g/mol, molecular weight distribution index 1.4-
2.2。
According to the present invention, in order to obtain the more excellent polylactic acid copolyesters of flexility and degradation property, preferably feelings
Under condition, the component a be M-phthalic acid, terephthalic acid (TPA), phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5- naphthalenedicarboxylic acid, 2,
7- naphthalenedicarboxylic acid, 4,4 '-biphenyl dicarboxylic acids and 3, one of 4 '-biphenyl dicarboxylic acids or a variety of, more preferably terephthalic acid (TPA),
One of M-phthalic acid and phthalic acid are a variety of, are still more preferably terephthalic acid (TPA).
Under preferable case, the component b is ethylene glycol, diethylene glycol (DEG), propylene glycol, butanediol, pentanediol, hexylene glycol, hexamethylene
One of pure and mild norbornane dimethanol of alkane two is a variety of, and one more preferably in butanediol, hexylene glycol and cyclohexane diol
Kind is a variety of, is still more preferably butanediol.
Under preferable case, the component c be succinic acid, succinic anhydride, adipic acid, adipic anhydride, azelaic acid, decanedioic acid,
Dodecanedioic acid, Isosorbide-5-Nitrae-cyclohexane diacid, 1, one of 2,4,5- hexamethylene tetracid dianhydrides and norbornane diacid or a variety of,
More preferably one of succinic acid, adipic acid and Isosorbide-5-Nitrae-cyclohexane diacid or a variety of are still more preferably adipic acid.
In accordance with the present invention it is preferred that the molar ratio of the component a, component b and component c are 1:2-5:0.8-3, preferably
1:2-4.5:0.8-2.5 more preferably 1:2-4.4:1-1.5.Wherein, component a and component b copolymerization is aromatic dibasic acid and two
First dehydration of alcohols is condensed to form corresponding ester structure, and the copolymerization of component c and component b are then binary acid and dihydric alcohol dehydrating condensation
Form corresponding ester structure.Above-mentioned molar ratio can represent the ratio of aromatic polyester structure and aliphatic polyester structure substantially as a result, no
The dosage for crossing usual component b is more on the high side, participates in subsequent reactions convenient for forming C-terminal.
According to the present invention, the chain extender is as described above, the bonding two molecules macromolecular of a molecule chain extender, from
And have the function that chain extension, the structure that chain extender provides its in polylactic acid copolyesters play the role of tie point.Preferably, the expansion
Chain agent is one of polyisocyanates, double oxazolines and epoxidized soybean oil or a variety of, preferably Isosorbide-5-Nitrae-hexamethylene-diisocyanate
Ester, 1,3- hexamethylene-diisocyanate, 1,2- hexamethylene-diisocyanate, 1- methyl -2,4- diisocyanate root conjunction-hexamethylene
Alkane, 1- methyl -2,6- diisocyanate root conjunction-hexamethylene, tetramethylene-diisocyanate, eight methylene-diisocyanates, ten
Methylene-diisocyanate, ten dimethylenes-diisocyanate, H6- 2,4- diisocyanate root closes toluene, 4,4'- diisocyanate
Root closes diphenyl methane, 2,4'- diisocyanate root closes diphenyl methane, 2,2'- diisocyanate root closes diphenyl methane, m- benzene
Dimethylene-diisocyanate, p- phenylenedimethylidyne-diisocyanate, 2,4- diisocyanate root close toluene, bis- isocyanide of 2,6-
Acid group closes toluene, isopropenyl dimethyl methyl for phenylene-diisocyanate, α, α, α ', α '-tetramethyl-two methylene of m- benzene
Base-diisocyanate, α, α, α ', the p- phenylenedimethylidyne-diisocyanate of α '-tetramethyl-, 1,6- hexa-methylene-diisocyanate
Ester, trimethyl cyclohexane-diisocyanate, tetramethyl hexane-diisocyanate, nonane-triisocyanate, 1- isocyanato--
3,3,5- trimethyl -5- isocyanato methylcyclohexane (isophorone-diisocyanate), 4,4'- diisocyanate root close-two
Cyclohexyl-methane and its monomethyl-and the substituted derivative of dimethyl-, 2,4'- diisocyanate root conjunction-dicyclohexyl methyl hydride and its
Monomethyl-and the substituted derivative of dimethyl-, 2,2'- diisocyanate root conjunction-dicyclohexyl methyl hydride and its monomethyl-and diformazan
The substituted derivative of base-, 2,2 '-(1,4- phenylene) bisoxazolines, 2,2 '-(1,3- phenylene) bisoxazolines and epoxy soybean
One of oil is a variety of
According to the present invention, polylactic acid copolyesters of the invention is regarded as containing aliphatic-aromatic cosegment, poly- cream
The linear copolyester of sour segment and the chain extender structures provided by chain extender, especially by aliphatic-aromatic cosegment, poly-
Lactic acid segment and the linear copolyester being made of the chain extender structures that chain extender provides, wherein under preferable case, the polylactic acid
The weight average molecular weight of copolyesters is 100,000-1,000,000g/mol, preferably 110,000-500,000g/mol, more preferably
It is still more preferably 130,000-170,000g/mol for 120,000-200,000g/mol；Molecular weight distributing index is
1.2-3 preferably 1.5-2.8.
Second aspect of the present invention provides a kind of preparation method of poly (lactic acid) composition, this method comprises:
(1) in the presence of Titanium series catalyst, component a, component b and component c are subjected to esterification；
(2) under vacuum conditions, esterification reaction mixture obtained in step (1) is subjected to pre-polymerization；
(3) in the presence of rare-earth metal catalyst, it is anti-that prepolymerization reaction mixture obtained in step (2) is subjected to polycondensation
It answers, obtains the product of aliphatic-aromatic copolymer；
(4) product of the resulting aliphatic-aromatic copolymer of step (3) and lactide monomer are subjected to copolyreaction；
(5) the resulting copolyreaction product of step (4) and chain extender are subjected to chain extending reaction, obtain polylactic acid copolyesters；
(6) polylactic acid copolyesters obtained by polylactic acid and step (5) is subjected to blending extrusion；
Wherein, the component a is C8-C20Aromatic acid, the C8-C20Aromatic acid acid anhydrides and institute
State C8-C20One of the ester of aromatic acid or a variety of；The component b is C2-C10Aliphatic dihydroxy alcohol and/or
C3-C10Cycloaliphatic diols；The component c is C2-C20Aliphatic dibasic acid, C5-C10Cycloaliphatic diacid and they
One of acid anhydrides or a variety of；
This method make resulting polylactic acid copolyesters be containing aliphatic-aromatic cosegment, polylactic acid chain segment and
By the linear copolyester for the chain extender structures that chain extender provides, and in the polylactic acid copolyesters, the aliphatic-aromatic is total
The content of poly chain section is 9-90 weight %, and the content of the polylactic acid chain segment is 9-90 weight %, and the chain extender structures contain
Amount is 0.1-5 weight %.
According to the present invention, as described above, under preferable case, this method makes in resulting polylactic acid copolyesters, described
The content of aliphatic-aromatic cosegment is 12-78.5 weight %, and the content of the polylactic acid chain segment is 22-80 weight %,
The content of the chain extender structures is 0.5-2 weight %.It is highly preferred that in resulting polylactic acid copolyesters, the aliphatic-virtue
The content of fragrant race's cosegment is 25-60 weight %, and the content of the polylactic acid chain segment is 40-70 weight %, the chain extender
The content of structure is 0.5-1.5 weight %.
According to the present invention, the component a, component b and component c are as described above, and details are not described herein the present invention.
According to the present invention, step (1)-(3) are by the product of obtained aliphatic-aromatic copolymer, containing big in the product
The aliphatic-aromatic copolymer of amount and a small amount of Titanium series catalyst and rare-earth metal catalyst, those skilled in the art can be with
The product for being interpreted as aliphatic-aromatic copolymer is made of aliphatic-aromatic copolymer and catalyst.Preferable case
Under, in the product, the content of the Titanium series catalyst is preferably 0.04-0.08 weight %, preferably 0.04-0.073 weight %,
More preferably 0.05-0.073 weight %.Preferably, the content of the rare-earth metal catalyst is 0.022-0.1 weight %, excellent
It is selected as 0.025-0.095 weight %, more preferably 0.028-0.055 weight %.
Wherein, the purpose of esterification of step (1) is in order to enable component a and component b, abundant between component c and component b
Ground esterification, it is preferable that on the basis of the integral molar quantity of the component a, component b and component c, in step (1), the titanium system catalysis
The dosage of agent is 0.01-0.04mol%, preferably 0.016-0.029mol%.The existing foot of the Titanium series catalyst of the amount ranges
Enough amounts meet the progress of the esterification, and promote aliphatic-aromatic copolymer and lactide monomer to be copolymerized, and will not
To in aliphatic-aromatic copolymer and lactide monomer copolymerization and the subsequent polylactic acid copolyesters product by chain extender chain extension
Introduce excessive metal element content.
According to the present invention, the purpose of step (2) is the product progress pre-polymerization in order to enable esterification obtained by step (1),
The prepolymer product of low molecular weight is obtained, the polycondensation of subsequent step (3) is facilitated.
In the case of, according to the invention it is preferred to, on the basis of the integral molar quantity of the component a, component b and component c, step
(3) in, the dosage of the rare-earth metal catalyst is 0.005-0.03mol%, preferably 0.008-0.015mol%.The dosage
The existing enough amounts of range meet the progress of polycondensation reaction described in step (3), and promote aliphatic-aromatic copolymer and third
Lactide monomers copolymerization, and will not be copolymerized to aliphatic-aromatic copolymer and lactide monomer and subsequent by chain extender chain extension
Polylactic acid copolyesters product in introduce excessive metal element content.
In the case of, according to the invention it is preferred to, the polycondensation reaction of the dosage and step (3) of the Titanium series catalyst in step (1)
In rare-earth metal catalyst dosage molar ratio be 1:0.4-1, more preferably 1:05-1.
In the case of, according to the invention it is preferred to, the Titanium series catalyst be butyl titanate titanium isopropoxide, titanium dioxide and
One of titanium tetrachloride is a variety of, more preferably one of butyl titanate, titanium dioxide and titanium isopropoxide or a variety of.
The Titanium series catalyst can be commercially available product, can also be made by conventional method, and details are not described herein for preparation method.
In the case of, according to the invention it is preferred to, the rare-earth metal catalyst is lanthanum acetylacetone, lanthanum chloride, isopropoxy
One of neodymium, 2,6- dibutyl -4- methylenedioxy phenoxy neodymium and Lanthanum Stearate are a variety of, more preferably lanthanum acetylacetone, isopropyl oxygen
One of base neodymium and Lanthanum Stearate are a variety of.The rare-earth metal catalyst can be commercially available product, can also pass through conventional side
Method be made, such as by document " Inorganic Chemistry 1970,9,2505,
J.Chem.Soc.Chem.Commun.1983,1499 " the middle methods recorded are made, the detailed process of preparation method, herein not
It repeats again.
In the case of, according to the invention it is preferred to, the condition of the esterification includes: that reaction temperature is 150-230 DEG C, reaction
Time is 2-7h.In more preferable situation, the esterification in step (1) includes: that component a and component b is first carried out the first esterification
Reaction, then the material after the first esterification is subjected to the second esterification with component c.Wherein, first esterification
Condition includes: that reaction temperature is 150-230 DEG C, reaction time 1-3h.The condition of second esterification includes: reaction temperature
Degree is 180-220 DEG C, reaction time 1-4h.It is highly preferred that the condition of first esterification includes: that reaction temperature is
180-200 DEG C, reaction time 2-3h.The condition of second esterification includes: that reaction temperature is 200-220 DEG C, reaction
Time is 2-4h.
In the case of, according to the invention it is preferred to, in step (2), the condition of the pre-polymerization include: absolute pressure be 500Pa with
Under, reaction temperature is 200-250 DEG C, reaction time 1-6h.It is highly preferred that the condition of the pre-polymerization includes: that absolute pressure is
400Pa hereinafter, reaction temperature be 200-240 DEG C, reaction time 1-3h.
Under preferable case, in step (3), the condition of the polycondensation reaction include: under absolute pressure 400Pa hereinafter, reaction
Temperature is 220-250 DEG C, reaction time 1-5h.It is highly preferred that the condition of the polycondensation reaction includes: that absolute pressure is
400Pa hereinafter, reaction temperature be 220-240 DEG C, reaction time 1-2h.
In the case of, according to the invention it is preferred to, above-mentioned steps (1)-(3) reaction all carries out under an inert atmosphere, the inertia
Atmosphere can be by one of nitrogen, helium, neon, argon gas etc. or a variety of offers.
According to the present invention it is possible to which vacuum volatilization drying will be carried out by product made from above-mentioned steps (1)-(3), removal is not
The monomer etc. of reaction, so that the product of the aliphatic-aromatic copolymer in the present invention is obtained, it is therefore, described in the present invention
Added most catalyst in step (1)-(3) reaction process is remained in the product of aliphatic-aromatic copolymer,
That is Titanium series catalyst and rare-earth metal catalyst, and in the product of the aliphatic-aromatic copolymer except Titanium series catalyst and
It is nearly all the aliphatic-aromatic copolymer outside rare-earth metal catalyst.As described above, those skilled in the art can be with
The product for being interpreted as aliphatic-aromatic copolymer of the invention is by Titanium series catalyst and rare-earth metal catalyst and fat
Race-aromatic copolymer composition.
According to the present invention, by the product of aliphatic-aromatic copolymer made from above-mentioned steps (1)-(3) in step (4)
In with lactide monomer carry out copolyreaction, so as to obtain aliphatic-aromatic-polylactic acid copolyesters.
Wherein, it is urged since the product of aliphatic-aromatic copolymer comes with a small amount of Titanium series catalyst and rare earth metal
Agent, so that Titanium series catalyst and rare-earth metal catalyst of the copolyreaction of step (4) actually in the part are deposited
Under lower progress, preferable case, the product of the aliphatic-aromatic copolymer and the dosage of lactide monomer make: with third
On the basis of the total weight of lactide monomers, the content of the Titanium series catalyst is 0.017-0.08 weight %, preferably 0.02-
0.073 weight %；The content of the rare-earth metal catalyst is 0.0033-0.1 weight %, preferably 0.01-0.095 weight
Measure %.
In addition, the aliphatic-aromatic copolymer product and the lactide monomer dosage within the above range
The purpose of the present invention can be realized.It is further preferred that on the basis of the lactide monomer of 100 parts by weight, the fat
The dosage of race-aromatic copolymer product is 15-110 parts by weight, more preferably 17-100 parts by weight, still more preferably for
35-100 parts by weight.
In the case of, according to the invention it is preferred to, in step (4), the condition of the copolyreaction includes: that reaction temperature is 150-
190 DEG C, reaction time 2-5h.It is highly preferred that it is 170-185 DEG C that the condition of the copolyreaction, which includes: reaction temperature, reaction
Time is 2.5-5h.
Wherein, under preferable case, the copolyreaction carries out in a nitrogen atmosphere, and is first passed through nitrogen to reaction system
Just start to carry out copolyreaction after 1-5h.
According to the present invention, it in step (5), needs the resulting copolyreaction product of step (4) and chain extender carrying out chain extension
Reaction, wherein the chain extender selects as described above, in a preferred embodiment of the invention, with
The lactide monomer of 100 parts by weight and the total weight of aliphatic-aromatic copolymer, the dosage of the chain extender are 0.1-5 weight
Measure part, preferably 0.5-1.5 parts by weight.
Wherein, under preferable case, in step (5), the condition of the chain extending reaction includes: that reaction temperature is 150-190 DEG C,
Reaction time is 20-100min.It is highly preferred that it is 170-185 DEG C that the condition of the chain extending reaction, which includes: reaction temperature, reaction
Time is 25-60min.
In the case of, according to the invention it is preferred to, after the chain extending reaction, retarder thinner is added and is diluted, then plus
Enter methanol to be precipitated, to obtain the precipitating of polylactic acid copolyesters product.The retarder thinner can for chloroform, methylene chloride,
One of tetrahydrofuran and n,N-Dimethylformamide are a variety of, preferably one in chloroform, methylene chloride and tetrahydrofuran
Kind is a variety of.
It is carried out due to the product and lactide monomer of the aliphatic-aromatic copolymer in the present invention in step (4)
Catalyst is not additionally added in copolyreaction, so that containing very small amount of metal in resulting polylactic acid copolyesters product
Element.For example, the metal element content in the polylactic acid copolyesters product is 0.02 weight % hereinafter, preferably 0.002-
0.015 weight % is still more preferably 0.004-0.008 weight %.
According to the present invention, in step (6), the polylactic acid is as described above, it is preferable that the polylactic acid and poly-
The weight ratio of lactic acid copolyesters is 100:10-100, preferably 100:15-60, more preferably 100:25-50.
According to the present invention, the blending extrusion can be in such a way that this field be conventional and condition, such as squeezes in twin-screw
It is squeezed out in machine out, the temperature of extruding pelletization for example can be 100-200 DEG C.Thus polylactic acid group of the invention can be obtained
Close object.
Third aspect present invention provides the poly (lactic acid) composition as made from above-mentioned preparation method.
The poly (lactic acid) composition is as described above, and it is the blending of polylactic acid and polylactic acid copolyesters that this method is resulting
Extruded product.
Fourth aspect present invention provides a kind of preparation method of biaxially stretched polylactic acid film, this method comprises:
(1) above-mentioned poly (lactic acid) composition is subjected to melting curtain coating slab, obtains polylactic acid slab；
(2) the polylactic acid slab is subjected to biaxial tension to form a film.
According to the present invention, melting curtain coating slab can carry out in casting machine, it is preferable that the temperature of the melting is
180-200℃.The melting be cast slab preferably so that the polylactic acid slab with a thickness of 200-500 μm.
In the case of, according to the invention it is preferred to, the biaxial tension is Synchronos method stretching, and it includes first will that the Synchronos method, which stretches,
Polylactic acid slab is preheated, and is then carried out MD and TD simultaneously and is stretched；The condition that the Synchronos method stretches includes: that draft temperature is
60-90 DEG C, MD stretching ratio is 2-6 times, 2-6 times of TD stretching ratio.
Fifth aspect present invention provides biaxially stretched polylactic acid film prepared by the above method.
The thickness of the biaxially stretched polylactic acid film is preferably 15-30 μm.
The biaxially stretched polylactic acid film mechanical strength with higher, and have preferable flexibility.The two-way drawing
The tensile strength of stretched polylactic acid film for example can be 27MPa or more, preferably 30MPa or more, more preferably 35MPa or more,
Preferably 35-50MPa；TD tensile strength for example can be 35MPa or more, preferably 40MPa or more, more preferably 40-
55MPa；MD break-draw rate for example can be 70% or more, preferably 100% or more, more preferably 150% or more, preferably
160-250%；TD break-draw rate for example can be 50% or more, preferably 80% or more, more preferably 90% or more, more excellent
It is selected as 95-200%；Light transmittance for example can be 85% or more, preferably 88-95%；Mist degree for example can be for 15% hereinafter, excellent
It is selected as 5-12%.
The present invention will be described in detail by way of examples below.
In following example:
Weight average molecular weight and molecular weight distributing index are measured using gel permeation chromatography (GPC), wherein with tetrahydro
Furans (THF) is solvent, on Waters-208 (band Waters 2410RI detector, 1.5mL/min flow velocity, 30 DEG C) instrument
Measurement, molecular weight are calibrated with the linear polystyrene standards of monodisperse；
Tensile strength and fracture tensile strength are measured according to the method recorded in GB/T 1040.2-2006；
Light transmittance and mist degree are measured according to the method recorded in GB/T 2410-2008.
Catalyst preparation example 1
Lanthanum chloride 9.37mmol is dissolved in the water of 50mL, the aqueous solution of the acetylacetone,2,4-pentanedione containing 56.2mmol is then added to
In, it is stirred at room temperature, the aqueous solution by the way that 2N KOH is added adjusts pH to neutrality.Reaction mixture stirring, filtering, in vacuum
It is dry at 60 DEG C, obtain lanthanum acetylacetone 4g.
Catalyst preparation example 2
Lanthanum chloride 9.37mmol is dissolved in the water of 50mL, the aqueous solution of the odium stearate containing 20mmol is then added to
In, it is stirred at room temperature, the aqueous solution by the way that 2N HCl is added adjusts pH to neutrality.Reaction mixture stirring, filtering, in vacuum
It is dry at 60 DEG C, obtain Lanthanum Stearate 11g.
Preparation example 1
2.2mol terephthalic acid (TPA), 5mol butanediol and 1.6mmol butyl titanate is (public purchased from Beijing chemical reagent
Department, chemistry are pure) it is added in reactor, and under nitrogen protection, it is heated with stirring to reflux, reaction temperature is controlled at 180 DEG C, and
The water steamed is collected, is almost collected to water and finishes (about reaction 2h).2.5mol succinic acid is additionally incorporated into system, continues to stir
It is heated to flowing back, reaction temperature is controlled at 200 DEG C, the water steamed is collected, until water, which is almost collected, finishes (about reaction 2h).Then,
By the system under conditions of temperature is 230 DEG C, absolute pressure is 400Pa pre-polymerization about 1h.Finally, being added into the system
0.85mmol lanthanum acetylacetone, temperature be 230 DEG C, absolute pressure be maintained at 200Pa it is below under the conditions of, polycondensation about 1h, lead to
Cross the aliphatic-aromatic copolyester P1 that vacuum volatilization is dried to obtain the white of 750g, weight average molecular weight 10,000g/
Mol, molecular weight distributing index 2.2, and in copolyesters P1, the content of butyl titanate is 0.060 weight %, levulinic
The content of ketone lanthanum is 0.041 weight %.
Preparation example 2
2.2mol terephthalic acid (TPA), 5mol butanediol and 1.6mmol butyl titanate are added in reactor, and in nitrogen
Under gas shielded, it is heated with stirring to reflux, reaction temperature is controlled at 200 DEG C, and collects the water steamed, is almost collected and is finished to water
(about reaction 2h).2.5mol succinic acid is additionally incorporated into system, continues to be heated with stirring to reflux, reaction temperature is controlled 220
DEG C, the water steamed is collected, until water, which is almost collected, finishes (about reaction 2h).It then, 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 be added 0.85mmol Lanthanum Stearate, temperature be 240 DEG C,
Absolute pressure be maintained at 200Pa it is below under the conditions of, polycondensation about 1.5h obtains 700g by the dry purification process of vacuum volatilization
White aliphatic-aromatic copolyester P2, weight average molecular weight 31,000g/mol, molecular weight distributing index 1.67,
And in copolyesters P2, the content of butyl titanate is 0.041 weight %, and the content of Lanthanum Stearate is 0.025 weight %.
Embodiment 1
The present embodiment is for illustrating poly (lactic acid) composition of the invention and preparation method thereof and biaxially stretched polylactic acid film
And preparation method thereof.
The L- lactide monomer (LLA) and 50g aliphatic-aromatic copolyester P1 of 50g is added separately in reactor, is mixed
5h will be purged with high pure nitrogen after closing uniformly, and reaction flask will be placed under nitrogen atmosphere after reacting 5h at 170 DEG C, 0.5g is added
1,6- hexamethylene diisocyanate, it is cooling and after reacting 30min, with chloroform dissolving mixt, and in anhydrous methanol into
Row precipitating, gained sediment is polylactic acid copolyesters A1 92g, weight average molecular weight, molecular weight distributing index, structural content
As shown in table 1.
The polylactic acid copolyesters A1 of the polylactic acid (nature works company trade mark 4042D) of 200g and 200g is added to
It is squeezed out in double screw extruder, wherein 100 DEG C, 170 DEG C, 170 DEG C, 160 are followed successively by from feed inlet to extrusion temperature of each section
℃.Dry materials after granulation, and be cast: the temperature for melting curtain coating is 190 DEG C, and discharge port temperature is 180 DEG C；Obtain thickness
About 450 μm of polylactic acid slab.
Gained polylactic acid slab is put into the stretching clamp of biaxial tension equipment, is film-made using synchro-draw, is wrapped
It includes: first preheating polylactic acid slab, then carry out MD simultaneously and stretch and TD stretching；Its condition includes: that preheating temperature is 80
DEG C, draft temperature is 80 DEG C, and 4 times of MD stretching ratio, TD stretching ratio is 4 times；Finally obtain the biaxial tension with a thickness of 25 μm
Polylactic acid film, performance are shown in Table 2.
Embodiment 2
The present embodiment is for illustrating poly (lactic acid) composition of the invention and preparation method thereof and biaxially stretched polylactic acid film
And preparation method thereof.
The L- lactide monomer (LLA) and 100g aliphatic-aromatic copolyester P1 of 50g is added separately in reactor,
5h will be purged with high pure nitrogen after mixing, and reaction flask will be placed under nitrogen atmosphere after reacting 3.5h at 180 DEG C, be added
2, the 4- toluene di-isocyanate(TDI) of 1.5g, and after reacting 40min, it is cooling, with chloroform dissolving mixt, and in anhydrous methanol into
Row precipitating, gained sediment is polylactic acid copolyesters A2 135g, weight average molecular weight, molecular weight distributing index, structural content
As shown in table 1.
The polylactic acid copolyesters A2 of the polylactic acid (nature works company trade mark 4042D) of 200g and 300g is added to
It is squeezed out in double screw extruder, wherein 100 DEG C, 170 DEG C, 170 DEG C, 160 are followed successively by from feed inlet to extrusion temperature of each section
℃.Dry materials after granulation, and be cast: the temperature for melting curtain coating is 190 DEG C, and discharge port temperature is 180 DEG C；Obtain thickness
About 450 μm of polylactic acid slab.
Gained polylactic acid slab is put into the stretching clamp of biaxial tension equipment, is film-made using synchro-draw, is wrapped
It includes: first preheating polylactic acid slab, then carry out MD simultaneously and stretch and TD stretching；Its condition includes: that preheating temperature is 80
DEG C, draft temperature is 80 DEG C, and 4 times of MD stretching ratio, TD stretching ratio is 4 times；Finally obtain the biaxial tension with a thickness of 25 μm
Polylactic acid film, performance are shown in Table 2.
Embodiment 3
The present embodiment is for illustrating poly (lactic acid) composition of the invention and preparation method thereof and biaxially stretched polylactic acid film
And preparation method thereof.
According to method described in embodiment 1, the difference is that, polylactic acid copolyesters is different, in preparation, using aliphatic-
Aromatic copolyester P2 replaces aliphatic-aromatic copolyester P1；Obtain polylactic acid copolyesters A3, weight average molecular weight, molecule
It is as shown in table 1 to measure profile exponent, structural content.
The biaxially stretched polylactic acid film with a thickness of 25 μm is finally obtained, performance is shown in Table 2.
Embodiment 4
The present embodiment is for illustrating poly (lactic acid) composition of the invention and preparation method thereof and biaxially stretched polylactic acid film
And preparation method thereof.
According to method described in embodiment 1, the difference is that, polylactic acid copolyesters is different, in preparation, 1,6- hexa-methylene
The dosage of diisocyanate is 0.2g, obtains polylactic acid copolyesters A4, weight average molecular weight, molecular weight distributing index, structure contain
Amount is as shown in table 1.
The biaxially stretched polylactic acid film with a thickness of 25 μm is finally obtained, performance is shown in Table 2.
Embodiment 5
The present embodiment is for illustrating poly (lactic acid) composition of the invention and preparation method thereof and biaxially stretched polylactic acid film
And preparation method thereof.
According to method described in embodiment 1, the difference is that, polylactic acid copolyesters is different, in preparation, 1,6- hexa-methylene
The dosage of diisocyanate is 4g, obtains polylactic acid copolyesters A5, weight average molecular weight, molecular weight distributing index, structural content
As shown in table 1.
The biaxially stretched polylactic acid film with a thickness of 25 μm is finally obtained, performance is shown in Table 2.
Since chain extender content is higher, containing the gel of high level in material, therefore GPC measurement in, macromolecular and
Gel component is filtered, and the material molecular weight of measurement will not be significantly raised.Also due to gel is more, the performance of film has instead
Declined.
Embodiment 6
The present embodiment is for illustrating poly (lactic acid) composition of the invention and preparation method thereof and biaxially stretched polylactic acid film
And preparation method thereof.
According to method described in embodiment 1, the difference is that, polylactic acid copolyesters is different, in preparation, L- lactide monomer
Dosage be 15g, the dosage of aliphatic-aromatic copolyester P1 is 85g；Obtain polylactic acid copolyesters A6, weight average molecular weight,
Molecular weight distributing index, structural content are as shown in table 1.
The biaxially stretched polylactic acid film with a thickness of 25 μm is finally obtained, performance is shown in Table 2.
Embodiment 7
The present embodiment is for illustrating poly (lactic acid) composition of the invention and preparation method thereof and biaxially stretched polylactic acid film
And preparation method thereof.
According to method described in embodiment 1, the difference is that, polylactic acid copolyesters is different, in preparation, L- lactide monomer
Dosage be 80g, the dosage of aliphatic-aromatic copolyester P1 is 20g；Obtain polylactic acid copolyesters A7, weight average molecular weight,
Molecular weight distributing index, structural content are as shown in table 1.
The biaxially stretched polylactic acid film with a thickness of 25 μm is finally obtained, performance is shown in Table 2.
Embodiment 8
The present embodiment is for illustrating poly (lactic acid) composition of the invention and preparation method thereof and biaxially stretched polylactic acid film
And preparation method thereof.
According to method described in embodiment 1, the difference is that, the dosage of polylactic acid copolyesters A1 is 50g, finally obtains thickness
For 25 μm of biaxially stretched polylactic acid film, performance is shown in Table 2.
Embodiment 9
The present embodiment is for illustrating poly (lactic acid) composition of the invention and preparation method thereof and biaxially stretched polylactic acid film
And preparation method thereof.
According to method described in embodiment 1, the difference is that, the dosage of polylactic acid copolyesters A1 is 100g, finally obtains thickness
The biaxially stretched polylactic acid film that degree is 25 μm, performance are shown in Table 2.
Embodiment 10
The present embodiment is for illustrating poly (lactic acid) composition of the invention and preparation method thereof and biaxially stretched polylactic acid film
And preparation method thereof.
According to method described in embodiment 1, the difference is that, the dosage of polylactic acid copolyesters A1 is 20g, finally obtains thickness
For 25 μm of biaxially stretched polylactic acid film, performance is shown in Table 2.
Embodiment 11
The present embodiment is for illustrating poly (lactic acid) composition of the invention and preparation method thereof and biaxially stretched polylactic acid film
And preparation method thereof.
According to method described in embodiment 1, the difference is that, the dosage of polylactic acid copolyesters A1 is 400g, finally obtains thickness
The biaxially stretched polylactic acid film that degree is 25 μm, performance are shown in Table 2.
Comparative example 1
According to method described in embodiment 1, the difference is that, polylactic acid copolyesters is different, in preparation, does not use 1,6- six
Methylene diisocyanate obtains polylactic acid copolyesters D1, weight average molecular weight, molecular weight distributing index, structural content such as table 1
It is shown.
Since molecular weight is too low, curtain coating and biaxial tension can not be carried out.
Comparative example 2
According to method described in embodiment 1, the difference is that, polylactic acid copolyesters is different, in preparation, 1,6- hexa-methylene
The dosage of diisocyanate is 10g, obtains polylactic acid copolyesters D2, weight average molecular weight, molecular weight distributing index, structural content
As shown in table 1.
The biaxially stretched polylactic acid film with a thickness of 25 μm is finally obtained, performance is shown in Table 2.
Since chain extender content is higher, containing the gel of high level in material, therefore GPC measurement in, macromolecular and
Gel component is filtered, and the material molecular weight of measurement will not be significantly raised.Also due to gel is more, the performance of film has instead
Declined.
Comparative example 3
According to method described in embodiment 1, the difference is that, polylactic acid copolyesters is different, in preparation, L- lactide monomer
Dosage be 5g, the dosage of aliphatic-aromatic copolyester P1 is 95g；Obtain polylactic acid copolyesters D3, weight average molecular weight,
Molecular weight distributing index, structural content are as shown in table 1.
The biaxially stretched polylactic acid film with a thickness of 25 μm is finally obtained, performance is shown in Table 2.
Comparative example 4
According to method described in embodiment 1, the difference is that, polylactic acid copolyesters is different, in preparation, L- lactide monomer
Dosage be 95g, the dosage of aliphatic-aromatic copolyester P1 is 5g；Obtain polylactic acid copolyesters D4, weight average molecular weight,
Molecular weight distributing index, structural content are as shown in table 1.
The biaxially stretched polylactic acid film with a thickness of 25 μm is finally obtained, performance is shown in Table 2.
Comparative example 5
According to method described in embodiment 1, the difference is that, polylactic acid copolyesters is not used, obtains pair with a thickness of 25 μm
To polylactic acid film is stretched, performance is shown in Table 2.
Table 1
Table 2
Note: noise is divided into A grades, B grades, C grades and D grades, wherein and D grades of noise is very small, and A grades of noise is very big,
In, noise size is A grades > B grades > C grades > D grades.
By above data as can be seen that soft low noise can be made in polylactic acid copolyesters and polylactic acid blend by the present invention
The biaxially stretched polylactic acid film of sound；This film has excellent light transmittance, lower mist degree, while having good mechanics
Performance.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (20)
1. a kind of poly (lactic acid) composition, which is characterized in that the composition contains polylactic acid and polylactic acid copolyesters, and the polylactic acid is total
Polyester is to be total to containing aliphatic-aromatic cosegment, polylactic acid chain segment and the linear of chain extender structures provided by chain extender
Polyester；
Wherein, the aliphatic-aromatic cosegment is made of aromatic polyester structure and aliphatic polyester structure；The fragrance is poly-
Ester structure is that the polyester construction formed is copolymerized by component a and component b, and the aliphatic polyester structure is to be copolymerized by component c and component b
The polyester construction of formation；
Wherein, the component a is C8-C20Aromatic acid, the C8-C20Aromatic acid acid anhydrides and the C8-
C20One of the ester of aromatic acid or a variety of；The component b is C2-C10Aliphatic dihydroxy alcohol and/or C3-C10's
Cycloaliphatic diols；The component c is C2-C20Aliphatic dibasic acid, C5-C10Cycloaliphatic diacid and their acid anhydrides in
It is one or more；
Wherein, on the basis of the weight of the polylactic acid copolyesters, the content of the aliphatic-aromatic cosegment is 9-90
Weight %, the content of the polylactic acid chain segment are 9-90 weight %, and the content of the chain extender structures is 0.1-5 weight %.
2. composition according to claim 1, wherein on the basis of the weight of the polylactic acid copolyesters, the fat
Race-aromatic copolyester segment content is 12-78.5 weight %, and the content of the polylactic acid chain segment is 22-80 weight %, described
The content of chain extender structures is 0.5-2 weight %；
Preferably, the content of the aliphatic-aromatic cosegment is 25-60 weight %, the content of the polylactic acid chain segment
For 40-70 weight %, the content of the chain extender structures is 0.5-1.5 weight %.
3. composition according to claim 1 or 2, wherein the molar ratio of the component a, component b and component c are 1:(2-
5): (0.8-3), preferably 1:(2-4.5): (0.8-2.5)；
Preferably, the component a is M-phthalic acid, terephthalic acid (TPA), phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5- naphthalene two
Formic acid, 2,7- naphthalenedicarboxylic acid, 4,4 '-biphenyl dicarboxylic acids and 3, one of 4 '-biphenyl dicarboxylic acids or a variety of, preferably to benzene two
One of formic acid, M-phthalic acid and phthalic acid are a variety of；The component b is ethylene glycol, diethylene glycol (DEG), propylene glycol, fourth
One of glycol, pentanediol, hexylene glycol, cyclohexane diol and norbornane dimethanol are a variety of, preferably butanediol, oneself two
One of pure and mild cyclohexane diol is a variety of；The component c is succinic acid, succinic anhydride, adipic acid, adipic anhydride, nonyl two
In acid, decanedioic acid, dodecanedioic acid, 1,4- cyclohexane diacid, 1,2,4,5- hexamethylene tetracid dianhydride and norbornane diacid
It is one or more, preferably one of succinic acid, adipic acid and Isosorbide-5-Nitrae-cyclohexane diacid or a variety of；
Preferably, the weight average molecular weight of the aliphatic-aromatic cosegment be 3,000-40,000g/mol, preferably 6,
000-35,000g/mol；Molecular weight distribution index is 1.2-2.5, preferably 1.4-2.2.
4. composition described in any one of -3 according to claim 1, wherein the chain extender is polyisocyanates, double evils
One of oxazoline and epoxidized soybean oil are a variety of, preferably Isosorbide-5-Nitrae-hexamethylene-diisocyanate ,-two isocyanide of 1,3- hexamethylene
Acid esters, 1,2- hexamethylene-diisocyanate, 1- methyl -2,4- diisocyanate root conjunction-hexamethylene, 1- methyl -2,6- diisocyanate
Root conjunction-hexamethylene, tetramethylene-diisocyanate, eight methylene-diisocyanates, decamethylene-diisocyanate, 12
Methylene-diisocyanate, H6- 2,4- diisocyanate root closes toluene, 4,4'- diisocyanate root closes diphenyl methane, 2,4'- bis-
Isocyanato- diphenyl methane, 2,2'- diisocyanate root close diphenyl methane, m- phenylenedimethylidyne-diisocyanate, p-
Phenylenedimethylidyne-diisocyanate, 2,4- diisocyanate root close toluene, 2,6- diisocyanate root closes toluene, isopropenyl diformazan
Base toluylene-diisocyanate, α, α, α ', the m- phenylenedimethylidyne-diisocyanate of α '-tetramethyl-, α, α, α ', α '-
P- phenylenedimethylidyne-the diisocyanate of tetramethyl-, 1,6- hexa-methylene-diisocyanate, trimethyl cyclohexane-diisocyanate
Ester, tetramethyl hexane-diisocyanate, nonane-triisocyanate, 1- isocyanato- -3,3,5- trimethyl -5- isocyano
Close hexahydrotoluene (isophorone-diisocyanate), 4,4'- diisocyanate root conjunction-dicyclohexyl methyl hydride and its monomethyl-and
The substituted derivative of dimethyl-, 2,4'- diisocyanate root conjunction-dicyclohexyl methyl hydride and its monomethyl-and dimethyl-are substituted
Derivative, 2,2'- diisocyanate root conjunction-dicyclohexyl methyl hydride and its monomethyl-and the substituted derivative of dimethyl-, 2,2 '-
(1,4- phenylene) bisoxazoline, 2,2 '-(1,3- phenylene) one of bisoxazolines and epoxidized soybean oil or a variety of.
5. composition described in any one of -4 according to claim 1, wherein the weight average molecular weight of the polylactic acid copolyesters
It is 100,000-1,000,000g/mol, preferably 110,000-500,000g/mol, more preferably 120,000-200,000g/
Mol is still more preferably 130,000-170,000g/mol；Molecular weight distributing index is 1.2-3, preferably 1.5-2.8.
6. composition described in any one of -5 according to claim 1, wherein the weight of the polylactic acid and polylactic acid copolyesters
Amount is than being 100:10-100, preferably 100:15-60, more preferably 100:25-50.
7. a kind of preparation method of poly (lactic acid) composition, which is characterized in that this method comprises:
(1) in the presence of Titanium series catalyst, component a, component b and component c are subjected to esterification；
(2) under vacuum conditions, esterification reaction mixture obtained in step (1) is subjected to pre-polymerization；
(3) in the presence of rare-earth metal catalyst, prepolymerization reaction mixture obtained in step (2) is subjected to polycondensation reaction,
Obtain the product of aliphatic-aromatic copolymer；
(4) product of the resulting aliphatic-aromatic copolymer of step (3) and lactide monomer are subjected to copolyreaction；
(5) the resulting copolyreaction product of step (4) and chain extender are subjected to chain extending reaction, obtain polylactic acid copolyesters；
(6) polylactic acid copolyesters obtained by polylactic acid and step (5) is subjected to blending extrusion；
Wherein, the component a is C8-C20Aromatic acid, the C8-C20Aromatic acid acid anhydrides and the C8-
C20One of the ester of aromatic acid or a variety of；The component b is C2-C10Aliphatic dihydroxy alcohol and/or C3-C10's
Cycloaliphatic diols；The component c is C2-C20Aliphatic dibasic acid, C5-C10Cycloaliphatic diacid and their acid anhydrides in
It is one or more；
This method makes resulting polylactic acid copolyesters be containing aliphatic-aromatic cosegment, polylactic acid chain segment and by expanding
The linear copolyester for the chain extender structures that chain agent provides, and in the polylactic acid copolyesters, the aliphatic-aromatic is copolymerized chain
The content of section is 9-90 weight %, and the content of the polylactic acid chain segment is 9-90 weight %, and the content of the chain extender structures is
0.1-5 weight %.
8. preparation method according to claim 7, wherein this method makes in resulting polylactic acid copolyesters, the rouge
Fat race-aromatic copolyester segment content is 12-78.5 weight %, and the content of the polylactic acid chain segment is 22-80 weight %, institute
The content for stating chain extender structures is 0.5-2 weight %；
Preferably, the content of the aliphatic-aromatic cosegment is 25-60 weight %, the content of the polylactic acid chain segment
For 40-70 weight %, the content of the chain extender structures is 0.5-1.5 weight %.
9. preparation method according to claim 7 or 8, wherein the molar ratio of the component a, component b and component c are 1:
(2-5): (0.8-3), preferably 1:(2-4.5): (0.8-2.5)；
Preferably, the component a is M-phthalic acid, terephthalic acid (TPA), phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5- naphthalene two
Formic acid, 2,7- naphthalenedicarboxylic acid, 4,4 '-biphenyl dicarboxylic acids and 3, one of 4 '-biphenyl dicarboxylic acids or a variety of, preferably to benzene two
One of formic acid, M-phthalic acid and phthalic acid are a variety of；The component b is ethylene glycol, diethylene glycol (DEG), propylene glycol, fourth
One of glycol, pentanediol, hexylene glycol, cyclohexane diol and norbornane dimethanol are a variety of, preferably butanediol, oneself two
One of pure and mild cyclohexane diol is a variety of；The component c is succinic acid, succinic anhydride, adipic acid, adipic anhydride, nonyl two
In acid, decanedioic acid, dodecanedioic acid, 1,4- cyclohexane diacid, 1,2,4,5- hexamethylene tetracid dianhydride and norbornane diacid
It is one or more, preferably one of succinic acid, adipic acid and Isosorbide-5-Nitrae-cyclohexane diacid or a variety of；
Preferably, step (3) makes the weight average molecular weight of resulting aliphatic-aromatic copolymer be 3,000-40,000g/
Mol, preferably 6,000-35,000g/mol；Molecular weight distribution index is 1.2-2.5, preferably 1.4-2.2.
10. the preparation method according to any one of claim 7-9, wherein in step (3), in the aliphatic-virtue
In the product of fragrant race's copolymer, the content of the Titanium series catalyst is 0.04-0.08 weight %, the rare-earth metal catalyst
Content is 0.022-0.1 weight %；
Preferably, on the basis of the integral molar quantity of the component a, component b and component c, in step (1), the Titanium series catalyst
Dosage be 0.01-0.04mol%, preferably 0.016-0.029mol%；
Preferably, on the basis of the integral molar quantity of the component a, component b and component c, in step (3), the rare earth metal is urged
The dosage of agent is 0.005-0.03mol%, preferably 0.008-0.015mol%；
Preferably, rare-earth metal catalyst in the polycondensation reaction of the dosage and step (3) of the Titanium series catalyst in step (1)
The molar ratio of dosage is 1:0.4-1；
Preferably, the Titanium series catalyst be one of butyl titanate, titanium isopropoxide, titanium dioxide and titanium tetrachloride or
It is a variety of；The rare-earth metal catalyst is lanthanum acetylacetone, lanthanum chloride, isopropoxy neodymium, 2,6- dibutyl -4- methylenedioxy phenoxy neodymium
With one of Lanthanum Stearate or a variety of.
11. preparation method according to any one of claims of claim 7-10, wherein the chain extender be polyisocyanates,
One of double oxazolines and epoxidized soybean oil are a variety of, preferably Isosorbide-5-Nitrae-hexamethylene-diisocyanate, 1,3- hexamethylene-two
Isocyanates, 1,2- hexamethylene-diisocyanate, 1- methyl -2,4- diisocyanate root conjunction-hexamethylene, 1- methyl -2,6- two are different
Cyanate radical conjunction-hexamethylene, tetramethylene-diisocyanate, eight methylene-diisocyanates, decamethylene-diisocyanate,
Ten dimethylenes-diisocyanate, H6- 2,4- diisocyanate root closes toluene, 4,4'- diisocyanate root closes diphenyl methane, 2,
4'- diisocyanate root closes diphenyl methane, 2,2'- diisocyanate root closes diphenyl methane, m- phenylenedimethylidyne-diisocyanate
Ester, p- phenylenedimethylidyne-diisocyanate, 2,4- diisocyanate root close toluene, 2,6- diisocyanate root closes toluene, isopropyl alkene
Base dimethyl methyl is for phenylene-diisocyanate, α, α, α ', the m- phenylenedimethylidyne-diisocyanate of α '-tetramethyl-, α, α,
P- phenylenedimethylidyne-the diisocyanate of α ', α '-tetramethyl-, 1,6- hexa-methylene-diisocyanate, trimethyl cyclohexane-two are different
Cyanate, tetramethyl hexane-diisocyanate, nonane-triisocyanate, 1- isocyanato- -3,3,5- trimethyl -5- isocyanide
Acid group closes hexahydrotoluene (isophorone-diisocyanate), 4,4'- diisocyanate root conjunction-dicyclohexyl methyl hydride and its single first
Base-and the substituted derivative of dimethyl-, 2,4'- diisocyanate root conjunction-dicyclohexyl methyl hydride and its monomethyl-and dimethyl-take
The substituted derivative of derivative, 2,2'- diisocyanate root conjunction-dicyclohexyl methyl hydride and its monomethyl-and dimethyl-in generation, 2,
2 '-(1,4- phenylene) bisoxazolines, 2,2 '-(1,3- phenylene) one of bisoxazolines and epoxidized soybean oil or a variety of.
12. the preparation method according to any one of claim 7-11, wherein in step (1), the esterification
Condition includes: that reaction temperature is 150-230 DEG C, reaction time 2-7h；
Preferably, in step (2), the condition of the pre-polymerization includes: that absolute pressure is 500Pa hereinafter, reaction temperature is 200-250
DEG C, reaction time 1-6h；
Preferably, in step (3), the condition of the polycondensation reaction includes: that absolute pressure is 400Pa hereinafter, reaction temperature is
220-250 DEG C, reaction time 1-5h；
Preferably, in step (4), the condition of the copolyreaction includes: that reaction temperature is 150-190 DEG C, reaction time 2-
5h；
Preferably, in step (5), the condition of the chain extending reaction includes: that reaction temperature is 150-190 DEG C, reaction time 20-
100min。
13. the preparation method according to claim 7 or 12, wherein in step (1), the esterification includes: first by group
Divide a and component b to carry out the first esterification, then the material after the first esterification is subjected to the second esterification with component c；Its
In, the condition of first esterification includes: that reaction temperature is 150-230 DEG C, reaction time 1-3h；Second esterification
The condition of reaction includes: that reaction temperature is 180-220 DEG C, reaction time 1-4h.
14. the preparation method according to any one of claim 7-13, wherein this method makes resulting polylactic acid total
The weight average molecular weight of polyester is 100,000-1,000,000g/mol, preferably 150,000-500,000g/mol；Molecular weight point
Cloth index is 1.2-3, preferably 1.5-2.8.
15. the preparation method according to any one of claim 7-14, wherein the polylactic acid and polylactic acid copolyesters
Weight ratio be 100:10-100, preferably 100:15-60, more preferably 100:25-50.
16. poly (lactic acid) composition made from the preparation method as described in any one of claim 7-15.
17. a kind of preparation method of biaxially stretched polylactic acid film, this method comprises:
(1) poly (lactic acid) composition described in any one of claim 1-6 and 16 is subjected to melting curtain coating slab, obtains poly- cream
Sour slab；
(2) the polylactic acid slab is subjected to biaxial tension to form a film.
18. according to the method for claim 17, wherein the temperature of the melting is 180-200 DEG C；
Preferably, the polylactic acid slab with a thickness of 200-500 μm；
Preferably, the biaxial tension is Synchronos method stretching, and it includes first preheating polylactic acid slab that the Synchronos method, which stretches,
MD and TD is then carried out simultaneously to stretch；The condition that the Synchronos method stretches includes: that draft temperature is 60-90 DEG C, MD stretching ratio
It is 2-6 times, 2-6 times of TD stretching ratio.
19. biaxially stretched polylactic acid film made from the method as described in claim 17 or 18.
20. biaxially stretched polylactic acid film according to claim 19, wherein the MD tensile strength of the film is 27MPa
More than, preferably 30MPa or more, more preferably 35MPa or more；TD tensile strength is 35MPa or more, preferably 40MPa or more；
MD break-draw rate is 70% or more, preferably 100% or more, more preferably 150% or more；TD break-draw rate be 50% with
On, preferably 80% or more, more preferably 90% or more；Light transmittance is 85% or more, preferably 88-95%；Mist degree is 15%
Hereinafter, preferably 5-12%.
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