CN109721699A - Polylactic acid copolyesters and preparation method thereof and biaxially stretched polylactic acid copolyester film and preparation method thereof - Google Patents
Polylactic acid copolyesters and preparation method thereof and biaxially stretched polylactic acid copolyester 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 polylactic acid copolyesters and preparation method thereof and biaxially stretched polylactic acid copolyester film and preparation method thereof.The polylactic acid copolyesters 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；The content of the aliphatic-aromatic cosegment 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 %.Biaxially stretched polylactic acid copolyester 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 polylactic acid copolyesters and preparation method thereof and two-way drawing
Stretched polylactic acid copolyester 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 the biaxially stretched polylactic acid copolyester film and preparation method thereof for having compared with high flexibility under higher mechanical property, Yi Jiju
Lactic acid copolyesters and preparation method thereof, the biaxially stretched polylactic acid copolyester film proof strength but also can reduce noise.
To achieve the goals above, one aspect of the present invention provides a kind of polylactic acid copolyesters, the polylactic acid copolyesters be containing
The linear copolyester of aliphatic-aromatic cosegment, polylactic acid chain segment and the chain extender structures provided by chain extender is provided；
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, the content of the aliphatic-aromatic cosegment is 9-90 weight %, the content of the polylactic acid chain segment
For 9-90 weight %, the content of the chain extender structures is 0.1-5 weight %.
Second aspect of the present invention provides a kind of preparation method of polylactic acid copolyesters, 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；
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 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 %.
Third aspect present invention provides the polylactic acid copolyesters as made from above-mentioned preparation method.
Fourth aspect present invention provides a kind of preparation method of biaxially stretched polylactic acid copolyester film, this method comprises:
(1) above-mentioned polylactic acid copolyesters is subjected to melting curtain coating slab, obtains polylactic acid copolyesters slab；
(2) the polylactic acid copolyesters slab is subjected to biaxial tension to form a film.
Fifth aspect present invention provides biaxially stretched polylactic acid copolyester film prepared by the above method.
Biaxially stretched polylactic acid copolyester film provided by the invention has in the case where guaranteeing higher mechanical property compared with highly-flexible
Property, so that proof strength but also noise can be reduced.
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 polylactic acid copolyesters, which is total containing aliphatic-aromatic
The linear copolyester of poly chain section, polylactic acid chain segment and the chain extender structures provided by chain extender；
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, the content of the aliphatic-aromatic cosegment is 9-90 weight %, the content of the polylactic acid chain segment
For 9-90 weight %, the content of the chain extender structures is 0.1-5 weight %.
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, just increases so poly- newborn
The molecular weight of acid-(aliphatic-aromatic cosegment)-polylactic acid, forms 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 the content of the aliphatic-aromatic cosegment is 12-78.5 weight
% is measured, the content of the polylactic acid chain segment is 22-80 weight %, and the content of the chain extender structures is 0.5-2 weight %.It is more excellent
Selection of land, the content of the aliphatic-aromatic cosegment are 25-60 weight %, and the content of the polylactic acid chain segment is 40-70
Weight %, the content of the chain extender structures are 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 polylactic acid copolyesters, 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；
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 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 %.
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 %.
Third aspect present invention provides the polylactic acid copolyesters as made from above-mentioned preparation method.
The polylactic acid copolyesters is as described above.
Fourth aspect present invention provides a kind of preparation method of biaxially stretched polylactic acid copolyester film, this method comprises:
(1) above-mentioned polylactic acid copolyesters is subjected to melting curtain coating slab, obtains polylactic acid copolyesters slab；
(2) the polylactic acid copolyesters slab is subjected to biaxial tension to form a film.
It according to the present invention, can be first by polylactic acid copolyesters extruding pelletization before carrying out melting curtain coating.The extruding pelletization
Condition can use the condition of this field routine, such as be squeezed out in double screw extruder, and the temperature of extruding pelletization is for example
It can be 100-200 DEG C.
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 copolyesters 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 copolyesters slab is preheated, and is then carried out MD and TD simultaneously and is stretched；The condition that the Synchronos method stretches includes: to stretch
Temperature is 60-90 DEG C, and MD stretching ratio is 2-6 times, 2-6 times of TD stretching ratio.
Fifth aspect present invention provides biaxially stretched polylactic acid copolyester film prepared by the above method.
The thickness of the biaxially stretched polylactic acid copolyester film is preferably 15-30 μm.
The biaxially stretched polylactic acid copolyester film mechanical strength with higher, and have preferable flexibility.It is described
The MD tensile strength of biaxially stretched polylactic acid copolyester film for example can be 24MPa or more, preferably 25MPa or more, it is more excellent
It is selected as 27-35MPa；TD tensile strength for example can be 20MPa or more, preferably 30MPa or more, preferably 40-45MPa；MD
Break-draw rate for example can be 200% or more, preferably 250% or more, more preferably 300% or more, preferably 350-
600%；TD break-draw rate for example can be 190% or more, preferably 220% or more, more preferably 300% or more, more into
One step is preferably 320-380%；Light transmittance for example can be 85% or more, preferably 88-95%；Mist degree for example can be 13%
Hereinafter, preferably 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 polylactic acid copolyesters and preparation method and biaxially stretched polylactic acid copolyesters of the invention
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.
It is squeezed out being added in double screw extruder after polylactic acid copolyesters A1 drying, wherein from feed inlet to extrusion
Temperature of each section is followed successively by 100 DEG C, 170 DEG C, 170 DEG C, 160 DEG C.Dry materials after granulation, and be cast: melt the temperature of curtain coating
Degree is 190 DEG C, and discharge port temperature is 180 DEG C；Obtain about 450 μm of thickness of polylactic acid copolyesters slab.
Gained polylactic acid copolyesters slab is put into the stretching clamp of biaxial tension equipment, using synchro-draw system
Film comprising: first polylactic acid copolyesters slab is preheated, MD is then carried out simultaneously and stretches and TD stretching；Its condition includes:
Preheating temperature is 80 DEG C, and draft temperature is 80 DEG C, and 4 times of MD stretching ratio, TD stretching ratio is 4 times；It finally obtains with a thickness of 25 μ
The biaxially stretched polylactic acid copolyester film of m, performance are shown in Table 2.
Embodiment 2
The present embodiment is for illustrating polylactic acid copolyesters and preparation method and biaxially stretched polylactic acid copolyesters of the invention
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.
It is squeezed out being added in double screw extruder after polylactic acid copolyesters A2 drying, wherein from feed inlet to extrusion
Temperature of each section is followed successively by 100 DEG C, 170 DEG C, 170 DEG C, 160 DEG C.Dry materials after granulation, and be cast: melt the temperature of curtain coating
Degree is 190 DEG C, and discharge port temperature is 180 DEG C；Obtain about 450 μm of thickness of polylactic acid copolyesters slab.
Gained polylactic acid copolyesters slab is put into the stretching clamp of biaxial tension equipment, using synchro-draw system
Film comprising: first polylactic acid copolyesters slab is preheated, MD is then carried out simultaneously and stretches and TD stretching；Its condition includes:
Preheating temperature is 80 DEG C, and draft temperature is 80 DEG C, and 4 times of MD stretching ratio, TD stretching ratio is 4 times；It finally obtains with a thickness of 25 μ
The biaxially stretched polylactic acid copolyester film of m, performance are shown in Table 2.
Embodiment 3
The present embodiment is for illustrating polylactic acid copolyesters and preparation method and biaxially stretched polylactic acid copolyesters of the invention
Film and preparation method thereof.
According to method described in embodiment 1, the difference is that, aliphatic-virtue is replaced using aliphatic-aromatic copolyester P2
Fragrant race's copolyesters P1；Obtain polylactic acid copolyesters A3, weight average molecular weight, molecular weight distributing index, structural content such as 1 institute of table
Show.
The biaxially stretched polylactic acid copolyester film with a thickness of 25 μm is finally obtained, performance is shown in Table 2.
Embodiment 4
The present embodiment is for illustrating polylactic acid copolyesters and preparation method and biaxially stretched polylactic acid copolyesters of the invention
Film and preparation method thereof.
According to method described in embodiment 1, the difference is that, the dosage of 1,6- hexamethylene diisocyanate is 0.2g, is obtained
To polylactic acid copolyesters A4, weight average molecular weight, molecular weight distributing index, structural content are as shown in table 1.
The biaxially stretched polylactic acid copolyester film with a thickness of 25 μm is finally obtained, performance is shown in Table 2.
Embodiment 5
The present embodiment is for illustrating polylactic acid copolyesters and preparation method and biaxially stretched polylactic acid copolyesters of the invention
Film and preparation method thereof.
According to method described in embodiment 1, the difference is that, the dosage of 1,6- hexamethylene diisocyanate is 4g, is obtained
Polylactic acid copolyesters A5, weight average molecular weight, molecular weight distributing index, structural content are as shown in table 1.
The biaxially stretched polylactic acid copolyester film with a thickness of 25 μm is finally obtained, performance is shown in Table 2.Due to chain extension
Agent content is higher, and containing the gel of high level in material, therefore in GPC measurement, macromolecular and gel component are filtered, and are surveyed
Fixed material molecular weight will not be significantly raised.Also due to gel is more, the performance of film is declined instead.
Embodiment 6
The present embodiment is for illustrating polylactic acid copolyesters and preparation method and biaxially stretched polylactic acid copolyesters of the invention
Film and preparation method thereof.
According to method described in embodiment 1, the difference is that, the dosage of L- lactide monomer is 15g, aliphatic-aromatic
The dosage of copolyesters P1 is 85g；Polylactic acid copolyesters A6 is obtained, weight average molecular weight, molecular weight distributing index, structural content are such as
Shown in table 1.
The biaxially stretched polylactic acid copolyester film with a thickness of 25 μm is finally obtained, performance is shown in Table 2.
Embodiment 7
The present embodiment is for illustrating polylactic acid copolyesters and preparation method and biaxially stretched polylactic acid copolyesters of the invention
Film and preparation method thereof.
According to method described in embodiment 1, the difference is that, the dosage of L- lactide monomer is 80g, aliphatic-aromatic
The dosage of copolyesters P1 is 20g；Polylactic acid copolyesters A7 is obtained, weight average molecular weight, molecular weight distributing index, structural content are such as
Shown in table 1.
The biaxially stretched polylactic acid copolyester film with a thickness of 25 μm is finally obtained, performance is shown in Table 2.
Comparative example 1
According to method described in embodiment 1, the difference is that, 1,6- hexamethylene diisocyanate is not used, poly- cream is obtained
Sour copolyesters D1, weight average molecular weight, molecular weight distributing index, structural content are as shown in table 1.
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, the dosage of 1,6- hexamethylene diisocyanate is 10g, is obtained
Polylactic acid copolyesters D2, weight average molecular weight, molecular weight distributing index, structural content are as shown in table 1.
The biaxially stretched polylactic acid copolyester film with a thickness of 25 μm is finally obtained, performance is shown in Table 2.Due to chain extension
Agent content is higher, and containing the gel of high level in material, therefore in GPC measurement, macromolecular and gel component are filtered, and are surveyed
Fixed material molecular weight will not be significantly raised.Also due to gel is more, the performance of film is declined instead.
Comparative example 3
According to method described in embodiment 1, the difference is that, the dosage of L- lactide monomer is 5g, and aliphatic-aromatic is total
The dosage of polyester P1 is 95g；Obtain polylactic acid copolyesters D3, weight average molecular weight, molecular weight distributing index, structural content such as table
Shown in 1.
The biaxially stretched polylactic acid copolyester 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, the dosage of L- lactide monomer is 95g, aliphatic-aromatic
The dosage of copolyesters P1 is 5g；Polylactic acid copolyesters D4 is obtained, weight average molecular weight, molecular weight distributing index, structural content are such as
Shown in table 1.
The biaxially stretched polylactic acid copolyester film with a thickness of 25 μm is finally obtained, 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 the poly- cream of soft low noise can be made in the resulting polylactic acid copolyesters of the present invention
Acid copolymer biaxially oriented film；This film has excellent light transmittance, lower mist degree, while having good mechanical property
Energy.
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 (18)
1. a kind of polylactic acid copolyesters, which is characterized in that the polylactic acid copolyesters be containing aliphatic-aromatic cosegment,
The linear copolyester of polylactic acid chain segment and the chain extender structures provided by chain extender；
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, the content of the aliphatic-aromatic cosegment is 9-90 weight %, and the content of the polylactic acid chain segment is 9-
90 weight %, the content of the chain extender structures are 0.1-5 weight %.
2. polylactic acid copolyesters according to claim 1, wherein the content of the aliphatic-aromatic cosegment is
12-78.5 weight %, the content of the polylactic acid chain segment are 22-80 weight %, and the content of the chain extension structure is 0.5-2 weight
Measure %；
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. polylactic acid copolyesters according to claim 1 or 2, wherein the molar ratio of the component a, component b and component c
For 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. polylactic acid copolyesters described in any one of -3 according to claim 1, wherein the chain extender is polyisocyanic acid
One of ester, double oxazolines and epoxidized soybean oil are a variety of, preferably Isosorbide-5-Nitrae-hexamethylene-diisocyanate, 1,3- hexamethylene-
Diisocyanate, 1,2- hexamethylene-diisocyanate, 1- methyl -2,4- diisocyanate root conjunction-hexamethylene, 1- methyl -2,6- two
Isocyanato--hexamethylene, tetramethylene-diisocyanate, eight methylene-diisocyanates, decamethylene-diisocyanate
Ester, 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 ,-two isocyanide of m- phenylenedimethylidyne
Acid esters, p- phenylenedimethylidyne-diisocyanate, 2,4- diisocyanate root close toluene, 2,6- diisocyanate root closes toluene, isopropyl
Alkenyl dimethyl methyl is for phenylene-diisocyanate, α, α, α ', the m- phenylenedimethylidyne-diisocyanate of α '-tetramethyl-, α,
α, α ', the p- phenylenedimethylidyne-diisocyanate of α '-tetramethyl-, 1,6- hexa-methylene-diisocyanate, trimethyl cyclohexane-two
Isocyanates, tetramethyl hexane-diisocyanate, nonane-triisocyanate, 1- isocyanato- -3,3,5- trimethyl -5- are different
Cyanate radical closes hexahydrotoluene (isophorone-diisocyanate), 4,4'- diisocyanate root conjunction-dicyclohexyl methyl hydride and its list
Methyl-and the substituted derivative of dimethyl-, 2,4'- diisocyanate root conjunction-dicyclohexyl methyl hydride and its monomethyl-and dimethyl-
Substituted derivative, 2,2'- diisocyanate root conjunction-dicyclohexyl methyl hydride and its monomethyl-and the substituted derivative of dimethyl-,
2,2 '-(1,4- phenylene) bisoxazolines, 2,2 '-(1,3- phenylene) one of bisoxazolines and epoxidized soybean oil or more
Kind.
5. polylactic acid copolyesters described in any one of -4 according to claim 1, wherein the weight of the polylactic acid copolyesters is equal
Molecular weight is 100,000-1,000,000g/mol, preferably 110,000-500,000g/mol, more preferably 120,000-
200,000g/mol, it is still more preferably 130,000-170,000g/mol；Molecular weight distributing index is 1.2-3, preferably
1.5-2.8。
6. a kind of preparation method of polylactic acid copolyesters, 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；
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 the content of the aliphatic-aromatic cosegment is 9-90 weight
% is measured, 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 %.
7. preparation method according to claim 6, 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 %.
8. preparation method according to claim 6 or 7, 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.
9. the preparation method according to any one of claim 6-8, 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.
10. the preparation method according to any one of claim 6-9, wherein the chain extender is polyisocyanates, double
One of oxazoline and epoxidized soybean oil are a variety of, and preferably Isosorbide-5-Nitrae-hexamethylene-diisocyanate, 1,3- hexamethylene-two are different
Cyanate, 1,2- hexamethylene-diisocyanate, 1- methyl -2,4- diisocyanate root conjunction-hexamethylene, two isocyanide of 1- methyl -2,6-
Acid group conjunction-hexamethylene, tetramethylene-diisocyanate, eight methylene-diisocyanates, decamethylene-diisocyanate, ten
Dimethylene-diisocyanate, H6- 2,4- diisocyanate root closes toluene, 4,4'- diisocyanate root closes diphenyl methane, 2,4'-
Diisocyanate root close 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 two
Methyl toluylene-diisocyanate, α, α, α ', the m- phenylenedimethylidyne-diisocyanate of α '-tetramethyl-, α, α, α ',
P- phenylenedimethylidyne-the diisocyanate of α '-tetramethyl-, 1,6- hexa-methylene-diisocyanate ,-two isocyanide of trimethyl cyclohexane
Acid esters, tetramethyl hexane-diisocyanate, nonane-triisocyanate, 1- isocyanato- -3,3,5- trimethyl -5- isocyanic acid
Root closes hexahydrotoluene (isophorone-diisocyanate), 4,4'- diisocyanate root conjunction-dicyclohexyl methyl hydride and its monomethyl-
Substituted derivative, 2,4'- diisocyanate root conjunction-dicyclohexyl methyl hydride and its monomethyl-and dimethyl-substitution with dimethyl-
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.
11. the preparation method according to any one of claim 6-10, 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。
12. the preparation method according to claim 6 or 11, 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.
13. the preparation method according to any one of claim 6-12, 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.
14. polylactic acid copolyesters made from the preparation method as described in any one of claim 6-13.
15. a kind of preparation method of biaxially stretched polylactic acid copolyester film, this method comprises:
(1) polylactic acid copolyesters described in any one of claim 1-5 and 14 is subjected to melting curtain coating slab, obtains poly- cream
Sour copolyesters slab；
(2) the polylactic acid copolyesters slab is subjected to biaxial tension to form a film.
16. according to the method for claim 15, wherein the temperature of the melting is 180-200 DEG C；
Preferably, the polylactic acid copolyesters slab with a thickness of 200-500 μm；
Preferably, the biaxial tension is that Synchronos method stretches, the Synchronos method stretch include first by polylactic acid copolyesters slab into
Row preheating then carries out MD and TD simultaneously and stretches；The condition that the Synchronos method stretches includes: that draft temperature is 60-90 DEG C, and MD is drawn
Stretching multiplying power is 2-6 times, 2-6 times of TD stretching ratio.
17. biaxially stretched polylactic acid copolyester film made from the method as described in claim 15 or 16.
18. biaxially stretched polylactic acid copolyester film according to claim 17, wherein the MD tensile strength of the film is
24MPa or more, preferably 25MPa or more；TD tensile strength is 20MPa or more, preferably 30MPa or more；MD break-draw rate
It is 200% or more, preferably 250% or more, more preferably 300% or more；TD break-draw rate is 190% or more, preferably
220% or more, more preferably 300% or more；Light transmittance is 85% or more, preferably 88-95%；Mist degree is 13% hereinafter, excellent
It is selected as 5-12%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280013A (en) * | 2020-11-10 | 2021-01-29 | 中北大学 | Preparation method of degradable heat-resistant copolyester |
| CN113603873A (en) * | 2021-08-23 | 2021-11-05 | 扬州惠通科技股份有限公司 | Production process of heat shrinkable film copolymer |
| CN113683744A (en) * | 2021-08-23 | 2021-11-23 | 扬州惠通科技股份有限公司 | Production method and application of hydrophilic copolymer containing polylactic acid chain segment |
| CN113968954A (en) * | 2021-12-13 | 2022-01-25 | 福建汇得新材料有限公司 | Degradable thermoplastic polyurethane elastomer and preparation method and application thereof |
| CN114634611A (en) * | 2022-04-20 | 2022-06-17 | 江苏铁锚玻璃股份有限公司 | Formula and preparation method of oriented stretch polyurethane plate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649045A (en) * | 2008-08-11 | 2010-02-17 | 中国科学院化学研究所 | Biodegradable polyester-polyester segmented copolymer, preparation method and application thereof |
| CN104592503A (en) * | 2013-10-30 | 2015-05-06 | 中国石油化工股份有限公司 | Polylactic acid ternary block copolyester and preparation method thereof |
| CN105623211A (en) * | 2014-10-28 | 2016-06-01 | 中国石油化工股份有限公司 | Polylactic acid composition and preparation method thereof |
| KR101644962B1 (en) * | 2016-02-03 | 2016-08-02 | 김석봉 | Biodegradable polylactide-based aliphatic/aromatic copolyester resin composition and method for preparing the same |
| CN105820321A (en) * | 2016-05-12 | 2016-08-03 | 杭州鑫富科技有限公司 | Biodegradable multi-block copolymer and preparation method thereof |
| CN107973907A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of more blocked aliphatic-aromatic series-polylactic acid copolyesters and preparation method thereof |
-
2017
- 2017-10-31 CN CN201711042244.6A patent/CN109721699B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649045A (en) * | 2008-08-11 | 2010-02-17 | 中国科学院化学研究所 | Biodegradable polyester-polyester segmented copolymer, preparation method and application thereof |
| CN104592503A (en) * | 2013-10-30 | 2015-05-06 | 中国石油化工股份有限公司 | Polylactic acid ternary block copolyester and preparation method thereof |
| CN105623211A (en) * | 2014-10-28 | 2016-06-01 | 中国石油化工股份有限公司 | Polylactic acid composition and preparation method thereof |
| KR101644962B1 (en) * | 2016-02-03 | 2016-08-02 | 김석봉 | Biodegradable polylactide-based aliphatic/aromatic copolyester resin composition and method for preparing the same |
| CN105820321A (en) * | 2016-05-12 | 2016-08-03 | 杭州鑫富科技有限公司 | Biodegradable multi-block copolymer and preparation method thereof |
| CN107973907A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of more blocked aliphatic-aromatic series-polylactic acid copolyesters and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| SEPEHR RAVATI，等: "High Performance Materials Based on a Self-Assembled Multiple-Percolated Ternary Blend", 《AICHE JOURNAL》 * |
| 徐百平主编: "《塑料挤出成型技术》", 31 August 2011, 中国轻工业出版社 * |
| 徐鼐: "《通用级聚乳酸的改性与加工成型》", 31 January 2016, 中国科学技术出版社 * |
| 焦剑主编: "《高分子物理》", 31 October 2015, 西北工业大学出版社 * |
| 祝桂香，等: "生物可降解脂肪芳香共聚酯增韧改性聚乳酸", 《石油化工》 * |
| 陈更新: "绿色环保型全降解聚乳酸改性的研制", 《塑料包装》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280013A (en) * | 2020-11-10 | 2021-01-29 | 中北大学 | Preparation method of degradable heat-resistant copolyester |
| CN113603873A (en) * | 2021-08-23 | 2021-11-05 | 扬州惠通科技股份有限公司 | Production process of heat shrinkable film copolymer |
| CN113683744A (en) * | 2021-08-23 | 2021-11-23 | 扬州惠通科技股份有限公司 | Production method and application of hydrophilic copolymer containing polylactic acid chain segment |
| CN113968954A (en) * | 2021-12-13 | 2022-01-25 | 福建汇得新材料有限公司 | Degradable thermoplastic polyurethane elastomer and preparation method and application thereof |
| CN114634611A (en) * | 2022-04-20 | 2022-06-17 | 江苏铁锚玻璃股份有限公司 | Formula and preparation method of oriented stretch polyurethane plate |
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