CN105585694B - A kind of flexible aliphatic aromatic PLA copolyesters product and preparation method thereof - Google Patents
A kind of flexible aliphatic aromatic PLA copolyesters product and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of aliphatic aromatic PLA copolyesters product, this method is by controlling the content of Titanium series catalyst and rare-earth metal catalyst, the product of the aliphatic aromatic copolymer of low rare earth Titanium series catalyst content, then the polymerization for the product initiation aliphatic aromatic PLA copolyesters product for passing through the aliphatic aromatic copolymer has been made.Present invention also offers aliphatic aromatic PLA copolyesters product made from the above method.The aliphatic aromatic PLA copolyesters product of the present invention has relatively low tenor, so as to have higher safety in utilization, and has higher pliability, overcomes the fragility defect of PLA script.
Description
Technical field
The present invention relates to a kind of flexible aliphatic-aromatic-PLA copolyesters product and preparation method thereof.
Background technology
It is known that PLA as a kind of Green Polymer Material, because it has biological source, therefore is opened energetically
Exhibition PLA industry can mitigate the pressure to fossil resources, and it also has benifit for alleviating greenhouse effects.But poly- breast
Sour material character is more crisp, toughness deficiency, therefore it is to improve the important directions of PLA performance that toughness reinforcing is carried out to PLA.Wherein,
It is one of method for improving PLA toughness that chain extension is carried out to PLA.But most of chain extenders are all containing isocyanic acid at present
Ester or epoxy ingredient, these compositions may produce poisonous and harmful substance during material degradation, be unfavorable for the big rule of material
Mould application.
Copolymerization is a kind of chain extension method of very effective plasticizing polylactic acid.As mentioned in patent application CN1911983A,
With any two kinds of progress ring-opening polymerisation in lactide, glycolide or caprolactone, hydroxy-end capped oligomer is obtained；Again by the hydroxyl
End-capped oligomeric carries out melt polymerization with linear polyester, it is possible to obtains the degradable high score for stent in shape memory pipe cavity
Sub- material.But in the patent application, preparing the ring-opening polymerisation of hydroxy-end capped oligomer needs to contain metal using high level
Catalyst, and carry out melt polymerization needs with linear polyester and carried out under diisocyanate coupling agent so that gained finally gathers
Compound still has higher tenor and diisocyanate content, and carries certain toxicity.
It can be seen that improving carrying out chain extension to PLA in the field of its fragility defect, the use of metallic catalyst generally be present
The problem of amount is high, using poisonous diisocyanate coupling agent, so that the polydactyl acid of gained is with certain toxicity.
The content of the invention
The purpose of the present invention be overcome it is existing need to add higher amount when carrying out copolymerization chain extension to PLA contain metal
Catalyst and/or diisocyanate coupling agent etc. carry so that the defects of polydactyl acid of gained carries higher toxicity
For it is a kind of do not use coupling agent and using lower content containing metallic catalyst carry out to PLA carry out be copolymerized chain extension change
Property a kind of aliphatic-aromatic-PLA copolyesters product preparation method and its obtained aliphatic-aromatic-poly- breast
Sour copolyesters product.
Generally, PLA copolyesters is prepared using lactide polymerization, is required for additionally adding lactide open loop and gathers
Catalyst needed for closing, the compound such as containing metallic zinc or tin class transition metal, so that obtained PLA is total to
The metallic element of higher amount is remained in polyester, has large effect to the safety in utilization of its product.However, the invention of the present invention
People has found, if use the end of the present invention as the aliphatic-aromatic copolymer initiation lactide and copolymerized therewith of hydroxyl,
, can drawing in rare earth-Titanium series catalyst of less dosage in the case of terminal hydroxyl using aliphatic-aromatic copolymer
Give, obtain a kind of copolymer-modified poly-lactic acid products of aliphatic-aromatic, i.e. aliphatic-aromatic-PLA copolyesters
Product.The polydactyl acid product of less tenor can be obtained using rare earth-Titanium series catalyst of less dosage, and more
Inventor is made it was unexpected that this polydactyl acid product also has extraordinary pliability, overcomes the fragility of PLA script
Defect.So as to complete the present invention.
Thus, the invention provides a kind of preparation method of aliphatic-aromatic-PLA copolyesters product, this method
Comprise the following steps：
(1) in the presence of Titanium series catalyst, component a, component b and component c are subjected to esterification；
(2) under vacuum, the esterification reaction mixture of gained in step (1) is subjected to pre-polymerization；
(3) in the presence of rare-earth metal catalyst, it is anti-that the prepolymerization reaction mixture of gained in step (2) is subjected to polycondensation
Should, the product of aliphatic-aromatic copolymer is obtained, wherein, it is described in the product of the aliphatic-aromatic copolymer
The content of Titanium series catalyst is 0.04-0.08 weight %, and the content of the rare-earth metal catalyst is 0.022-0.1 weight %；
(4) product of the aliphatic-aromatic copolymer obtained by step (3) and lactide monomer are subjected to copolyreaction,
Wherein, the product of the aliphatic-aromatic copolymer and the dosage of lactide monomer cause：With the gross weight of lactide monomer
On the basis of, the content of the Titanium series catalyst is 0.017-0.08 weight %, and the content of the rare-earth metal catalyst is
0.0033-0.1 weight %；
Wherein, the component a is C8-C20Aromatic acid, the C8-C20Aromatic acid acid anhydrides and institute
State C8-C20Aromatic acid ester in one or more；The component b is C2-C10Aliphatic dihydroxy alcohol and/or
C3-C10Cycloaliphatic diols；The component c is C2-C20Aliphatic dibasic acid, C3-C10Cycloaliphatic diacid and they
Acid anhydrides in one or more.
Present invention also offers the aliphatic-aromatic obtained by the above method-PLA copolyesters product.
By using the method for the present invention, due in step (1)-product of aliphatic-aromatic copolymer made from (3)
Rare earth-Titanium series catalyst containing less dosage, and obtained aliphatic-aromatic copolymer has active end hydroxyl
Base, it can then use the product and lactide of the aliphatic-aromatic copolymer for containing a small amount of rare earth-Titanium series catalyst using this
Monomer carries out copolyreaction, so as to be copolymerized under this small amount of rare earth-Titanium series catalyst initiation, using aliphatic-aromatic
Under conditions of the active terminal hydroxy group of thing, obtain a kind of copolymer-modified poly-lactic acid products of aliphatic-aromatic, i.e., it is fatty
Race-aromatic series-PLA copolyesters product.There is the aliphatic-aromatic-PLA copolyesters product relatively low metal to contain
Amount, so as to have higher safety in utilization, and there is higher pliability, overcome the fragility defect of PLA script.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of preparation method of aliphatic-aromatic-PLA copolyesters product, and this method includes following
Step：
(1) in the presence of Titanium series catalyst, component a, component b and component c are subjected to esterification；
(2) under vacuum, the esterification reaction mixture of gained in step (1) is subjected to pre-polymerization；
(3) in the presence of rare-earth metal catalyst, it is anti-that the prepolymerization reaction mixture of gained in step (2) is subjected to polycondensation
Should, the product of aliphatic-aromatic copolymer is obtained, wherein, it is described in the product of the aliphatic-aromatic copolymer
The content of Titanium series catalyst is 0.04-0.08 weight %, and the content of the rare-earth metal catalyst is 0.022-0.1 weight %；
(4) product of the aliphatic-aromatic copolymer obtained by step (3) and lactide monomer are subjected to copolyreaction,
Wherein, the product of the aliphatic-aromatic copolymer and the dosage of lactide monomer cause：With the gross weight of lactide monomer
On the basis of, the content of the Titanium series catalyst is 0.017-0.08 weight %, and the content of the rare-earth metal catalyst is
0.0033-0.1 weight %；
Wherein, the component a is C8-C20Aromatic acid, the C8-C20Aromatic acid acid anhydrides and institute
State C8-C20Aromatic acid ester in one or more；The component b is C2-C10Aliphatic dihydroxy alcohol and/or
C3-C10Cycloaliphatic diols；The component c is C2-C20Aliphatic dibasic acid, C3-C10Cycloaliphatic diacid and they
Acid anhydrides in one or more.
According to the present invention, 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 up of aliphatic-aromatic copolymer and catalyst.Preferable case
Under, in the product, the content of the Titanium series catalyst is preferably 0.04-0.073 weight %, and more preferably 0.05-0.073 is heavy
Measure %.Preferably, the content of the rare-earth metal catalyst is 0.025-0.095 weight %, more preferably 0.028-0.055 weights
Measure %.
In the case of, according to the invention it is preferred to, the dosage of the Titanium series catalyst in step (1) and the prepolymerization reaction of step (3)
In rare-earth metal catalyst dosage mol ratio be 1：0.4-1, more preferably 1：05-1.
Wherein, the construction unit of the aliphatic-aromatic copolymer has structure shown in formula (1)：
Wherein, Ar is the group with phenyl ring, naphthalene nucleus or anthracene nucleus；M is preferably 1-20 integer；N is preferably the whole of 1-16
Number；T is preferably 1-20 integer；X can be 1-100 integer, preferably 15-60 integer；Y can be 1-100 integer,
Preferably 15-60 integer.
Under preferable case, Ar is following aryl：
Wherein, R1、R2、R3、R4、R5And R6It is each independently hydrogen, C1-C4 alkyl, F, Cl ,-NO2,-CN or-OR7, its
In, R7For C1-C4 alkyl.
In the case of most preferably, Ar isWherein, R1And R2It is same as above.
According to the present invention, in order to obtain the preferably transparency and flexility, under preferable case, the aliphatic-fragrance
The weight average molecular weight of race's copolymer is 3000-40000, molecular weight distribution index 1.2-2.5.It is highly preferred that the aliphatic-
The weight average molecular weight of aromatic copolymer is 6000-35000, molecular weight distribution index 1.4-2.2.
According to the present invention, in order to obtain the more excellent aliphatic-aromatic copolymer of flexility and degradation property,
It is M-phthalic acid, terephthalic acid (TPA), phthalic acid, NDA, 1,5- naphthalenes in the component a under preferable case
Dioctyl phthalate, 2,7- naphthalenedicarboxylic acids, 4,4 '-biphenyl dicarboxylic acid and 3, the one or more in 4 '-biphenyl dicarboxylic acid, more preferably pair
One or more in phthalic acid, M-phthalic acid and phthalic acid, it is still more preferably terephthalic acid (TPA).
Under preferable case, the component b be selected from ethylene glycol, diethylene glycol (DEG), propane diols, butanediol, pentanediol, hexylene glycol,
In one or more in cyclohexane diol and norbornane dimethanol, more preferably butanediol, hexylene glycol and cyclohexane diol
One or more, be still more preferably butanediol.
Under preferable case, the component c be succinic acid, succinic anhydride, adipic acid, adipic anhydride, azelaic acid, decanedioic acid,
One or more in dodecanedioic acid, Isosorbide-5-Nitrae-cyclohexane diacid, 1,2,4,5- hexamethylene tetracarboxylic dianhydrides and norbornane diacid,
One or more more preferably in succinic acid, adipic acid and Isosorbide-5-Nitrae-cyclohexane diacid, are still more preferably adipic acid.
According to the present invention, although the reaction of component a, component b and component c progress step (1)-(3) can be obtained described
The product of aliphatic-aromatic copolymer, in order that component a, component b and component c reaction it is more abundant and obtain have give birth to
The aliphatic-aromatic copolymer of thing degradation property, under preferable case, the component a, component b and component c mol ratio are 1：
(2-5)：(0.8-3), more preferably 1：(2-4.5)：(0.8-2.5), it is still more preferably 1：(2-4.4)：(1-1.5).
According to the present invention, the dosage of the Titanium series catalyst is not particularly limited, as long as being capable of catalytic step (1)
In the esterification progress, and promote aliphatic-aromatic copolymer and lactide monomer to be copolymerized, but in order to
There is the progress that enough amounts meet the esterification, and promote aliphatic-aromatic copolymer to be copolymerized with lactide monomer,
It will not give aliphatic-aromatic copolymer the PLA copolymer-modified with the aliphatic-aromatic of lactide monomer copolymerization again
Introduce excessive metal element content in product, under preferable case, using the component a, component b and component c integral molar quantity as
Benchmark, in step (1), the dosage of the Titanium series catalyst is 0.01-0.04mol%, more preferably 0.016-0.029mol%.
According to the present invention, similarly, for the progress for there are enough amounts to meet polycondensation reaction described in step (3), and promote
Enter aliphatic-aromatic copolymer to be copolymerized with lactide monomer, aliphatic-aromatic copolymer and lactide monomer will not be given again
Introduce excessive metal element content in the copolymer-modified poly-lactic acid products of the aliphatic-aromatic of copolymerization, under preferable case,
On the basis of the component a, component b and component c integral molar quantity, the dosage of the rare-earth metal catalyst is 0.005-
0.03mol%, more preferably 0.008-0.015mol%.
In the case of, according to the invention it is preferred to, the Titanium series catalyst is butyl titanate, titanium isopropoxide, titanium dioxide
With the one or more in titanium tetrachloride, more preferably one kind or more in butyl titanate, titanium isopropoxide and titanium dioxide
Kind.The Titanium series catalyst can be commercially available product, can also be made by conventional method.
In the case of, according to the invention it is preferred to, the rare-earth metal catalyst is lanthanum acetylacetone, anhydrous lanthanum chloride, isopropyl
It is one or more in epoxide neodymium, 2,6- dibutyl -4- methylenedioxy phenoxies neodymium and Lanthanum Stearate, more preferably lanthanum acetylacetone, different
One or more in propoxyl group neodymium and Lanthanum Stearate.The rare-earth metal catalyst can be commercially available product, can also be by normal
Rule method is made, for example, by document " Inorganic Chemistry 1970,9,2505,
Method described in J.Chem.Soc.Chem.Commun.1983,1499 " is made.
In the case of, according to the invention it is preferred to, the condition of the esterification includes：Reaction temperature is 150-230 DEG C, reaction
Time is 2-7h.In the case of more preferably, the esterification in step (1) includes：Component a and component b is first subjected to the first esterification
Reaction, then the material after the first esterification and component c are subjected to the second esterification.Wherein, under preferable case, described first
The condition of esterification includes：Reaction temperature is 150-230 DEG C, reaction time 1-3h.The condition of second esterification
Including：Reaction temperature is 180-220 DEG C, reaction time 1-4h.It is highly preferred that the condition of first esterification includes：
Reaction temperature is 180-200 DEG C, reaction time 2-3h.The condition of second esterification includes：Reaction temperature is 200-
220 DEG C, reaction time 2-4h.
In the case of, according to the invention it is preferred to, in step (2), the condition of the pre-polymerization includes：Absolute pressure be 500Pa with
Under, reaction temperature is 200-250 DEG C, reaction time 1-6h.More preferably, the condition of the pre-polymerization includes：Absolute pressure is
Below 400Pa, reaction temperature are 200-240 DEG C, reaction time 1-3h.
Under preferable case, in step (3), the condition of the polycondensation reaction includes：Below 400Pa under absolute pressure, reaction
Temperature is 220-250 DEG C, reaction time 1-5h.It is highly preferred that the condition of the polycondensation reaction includes：Absolute pressure is
Below 400Pa, reaction temperature are 220-240 DEG C, reaction time 1-2h.
In the case of, according to the invention it is preferred to, the reaction of above-mentioned steps (1)-(3) is all carried out under nitrogen protection.
According to the present invention, above-mentioned steps (1)-product made from (3) will be passed through and carry out vacuum volatilization drying, remove unreacted
Monomer etc., so as to obtain the product of the aliphatic-aromatic copolymer in the present invention, therefore, the fat in the present invention
The catalyst added in step (1)-(3) course of reaction, i.e. Titanium series catalyst are remained with the product of race-aromatic copolymer
And rare-earth metal catalyst, and Titanium series catalyst and catalyzing of rare-earth metal are removed in the product of the aliphatic-aromatic copolymer
Nearly all it is the aliphatic-aromatic copolymer outside agent.As described above, it will be appreciated by those skilled in the art that being the present invention
The product of aliphatic-aromatic copolymer be to be total to by Titanium series catalyst and rare-earth metal catalyst and aliphatic-aromatic
Polymers forms.
According to the present invention, by the product of above-mentioned steps (1)-aliphatic-aromatic copolymer made from (3) in step (4)
In with lactide monomer carry out copolyreaction, so as to obtain the production of the aliphatic-aromatic-PLA copolyesters of the present invention
Product.
Wherein, because the product of aliphatic-aromatic copolymer comes with a small amount of Titanium series catalyst and rare earth metal is urged
Agent, so that Titanium series catalyst and rare-earth metal catalyst of the copolyreaction of step (4) actually in the part are deposited
Under lower progress, preferable case, the product of the aliphatic-aromatic copolymer and the dosage of lactide monomer cause：With third
On the basis of the gross weight of lactide monomers, the content of the Titanium series catalyst is 0.02-0.073 weight %, and the rare earth metal is urged
The content of agent is 0.01-0.095 weight %.
In addition, the aliphatic-aromatic copolymer product and the lactide monomer dosage within the above range
The purpose of the present invention can be achieved.It is further preferred that on the basis of the lactide monomer of 100 parts by weight, the fat
The dosage of the product of race-aromatic copolymer is 15-110 parts by weight, more preferably 17-100 parts by weight, still more preferably for
35-100 parts by weight.
In the case of, according to the invention it is preferred to, in step (4), the condition of the copolyreaction includes：Reaction temperature is 150-
190 DEG C, reaction time 2-5h.It is highly preferred that the condition of the copolyreaction includes：Reaction temperature is 170-185 DEG C, reaction
Time is 2.5-5h.
Wherein, under preferable case, the copolyreaction is carried out in a nitrogen atmosphere, and is first passed through nitrogen to reaction system
Copolyreaction is just proceeded by after 1-5h.
In the case of, according to the invention it is preferred to, after the polymerisation terminates, add retarder thinner and be diluted, then add
Enter methanol to be precipitated, to obtain the precipitation of aliphatic-aromatic-PLA copolyesters product.The retarder thinner can be
One or more in chloroform, dichloromethane, tetrahydrofuran and DMF, preferably chloroform, dichloromethane and
One or more in tetrahydrofuran.
Present invention also offers as the aliphatic-aromatic obtained by the above method-PLA copolyesters product.
Carried out due to the product of the aliphatic-aromatic copolymer in the present invention in step (4) with lactide monomer
Catalyst is not additionally added in copolyreaction so that contain in the aliphatic-aromatic of gained-PLA copolyesters product
Very small amount of metallic element.For example, the metal element content in the aliphatic-aromatic-PLA copolyesters product is
Below 0.02 weight %, preferably 0.002-0.015 weight %, it is still more preferably 0.004-0.008 weight %.
According to the present invention, the product of the aliphatic-aromatic copolymer in step (4) is total to what lactide monomer was carried out
Poly- reaction is a kind of random copolymerization, i.e., between aliphatic-aromatic copolymer therein, aliphatic-aromatic copolymer with
Between lactide monomer, it can polymerize between lactide monomer, and the product that they polymerize can also carry out ester again
Exchange, so as to which aliphatic-aromatic-PLA copolyesters product of present invention gained is also that one kind is total to through aliphatic-aromatic
The atactic polymer of polymerized PLA.
Also, using the present invention method made from aliphatic-aromatic-PLA copolyesters product, except with containing
Less amount of metallic element and have outside the advantages of higher safety in utilization, more it was unexpectedly observed that pass through the present invention method
Obtained aliphatic-aromatic-PLA copolyesters product also has extraordinary pliability, preferably overcomes PLA original
This fragility defect.
The present invention will be described in detail by way of examples below.
Following catalyst preparation example, preparation example, prepare in comparative example, embodiment and comparative example,
Wherein, in aliphatic-aromatic-PLA copolyesters, PLA/copolyesters weight ratio is by nuclear magnetic resonance side
What method measured；
Weight average molecular weight and molecular weight distributing index are determined using gel permeation chromatography (GPC), wherein, with tetrahydrochysene
Furans is solvent, is measured on Waters-208 (the band RI detectors of Waters 2410,1.5mL/min flow velocitys, 30 DEG C) instrument,
Molecular weight is calibrated with the linear polystyrene standards of single dispersing；
Tensile strength and fracture tensile strength are that the method according to described in GB/T 1040.2-2006 measures.
Catalyst preparation example 1
The excessive dissolving with hydrochloric acid of 10g lanthanas, 0.5g NH is added after heating concentration4Cl, careful heating remove excessive
HCl, after obtained solid is dried, study and add in quartzy sublimation pipe, solid obtained by vacuum sublimation is lanthanum chloride.
Catalyst preparation example 2
Lanthanum chloride 9.37mmol is dissolved in 50mL water, is then added to the aqueous solution of the acetylacetone,2,4-pentanedione containing 56.2mmol
In, it is stirred at room temperature, the aqueous solution by adding 2N KOH adjusts pH to neutrality.Reactant mixture stirs, filtering, in vacuum
Dried at 60 DEG C, obtain lanthanum acetylacetone 4g.
Catalyst preparation example 3
Lanthanum chloride 9.37mmol is dissolved in 50mL water, is then added to the aqueous solution of the odium stearate containing 20mmol
In, it is stirred at room temperature, the aqueous solution by adding 2N HCl adjusts pH to neutrality.Reactant mixture stirs, filtering, in vacuum
Dried at 60 DEG C, obtain Lanthanum Stearate 11g.
Preparation example 1
2.2mol terephthalic acid (TPA)s, 5mol butanediols and 1.6mmol butyl titanates is (public purchased from Beijing chemical reagent
Department, chemistry are pure) it is added in reactor, and under nitrogen protection, backflow is heated with stirring to, reaction temperature is controlled at 180 DEG C, and
The water steamed is collected, treats that water is almost collected and finishes and (about react 2h).2.5mol succinic acid is it is possible to additionally incorporate into system, continues to stir
It is heated to flowing back, reaction temperature is controlled at 200 DEG C, is collected the water steamed, is almost collected to water and finish and (about react 2h).Then,
By the system under conditions of temperature is 230 DEG C, absolute pressure is 400Pa pre-polymerization about 1h.Finally, added into the system
0.85mmol lanthanum acetylacetones, under conditions of temperature is 230 DEG C, absolute pressure is maintained at below 200Pa, polycondensation about 1h, lead to
Cross and vacuumize devolatilization and obtain 750g white aliphatic-aromatic copolyester P1, its weight average molecular weight is 10000, molecular weight
Profile exponent is 2.2, and in copolyesters P1, and the content of butyl titanate is 0.06 weight %, the content of lanthanum acetylacetone
For 0.041 weight %.
Preparation example 2
2.2mol terephthalic acid (TPA)s, 5mol butanediols and 1.6mmol butyl titanates are added in reactor, and in nitrogen
Under gas shielded, backflow is heated with stirring to, reaction temperature is controlled at 200 DEG C, and collects the water steamed, is treated that water is almost collected and is finished
(about reacting 2h).2.5mol succinic acid is it is possible to additionally incorporate into system, continues to be heated with stirring to backflow, reaction temperature is controlled 220
DEG C, the water steamed is collected, is almost collected to water and is finished and (about react 2h).Then, it is 240 DEG C, absolute pressure in temperature by the system
Power is pre-polymerization about 1h under conditions of 400Pa.Finally, into the system add 0.85mmol Lanthanum Stearates, temperature be 240 DEG C,
Absolute pressure is maintained under conditions of below 200Pa, polycondensation about 1.5h, and 700g white is obtained by vacuumizing devolatilization under melting
Aliphatic-aromatic copolyester P2, its weight average molecular weight is 31000, molecular weight distributing index 1.67, and the copolyesters
In P2, the content of butyl titanate is 0.041 weight %, and the content of Lanthanum Stearate is 0.025 weight %.
Preparation example 3
0.3mol terephthalic acid (TPA)s, 1.35mol butanediols and 0.7mmol titanium dioxide is (public purchased from Beijing chemical reagent
Department, chemistry are pure) it is added in reactor, and under nitrogen protection, backflow is heated with stirring to, reaction temperature is controlled at 180 DEG C, and
The water steamed is collected, treats that water is almost collected and finishes and (about react 2h).0.75mol adipic acids are it is possible to additionally incorporate into system, continue to stir
Mix and be heated to flowing back, reaction temperature is controlled at 200 DEG C, is collected the water steamed, is almost collected to water and finish and (about react 2h).So
Afterwards, by the system under conditions of temperature is 180 DEG C, absolute pressure is 500Pa pre-polymerization about 1h.Finally, added into the system
0.35mmol anhydrous lanthanum chlorides, under conditions of temperature is 220 DEG C, absolute pressure is maintained at below 150Pa, polycondensation about 1h, lead to
Cross and vacuumize devolatilization and obtain 230g yellowish aliphatic-aromatic copolyester P3, its weight average molecular weight is 35000, molecule
It is 1.95 to measure profile exponent, and in copolyesters P3, the content of titanium dioxide is 0.041 weight %, and the content of lanthanum chloride is
0.053 weight %.
Prepare comparative example 1
0.4mol terephthalic acid (TPA)s, 0.96mol butanediols and 0.5mmol butyl titanates (are purchased from Beijing chemical reagent
Company, chemistry are pure) it is added in reactor, and under nitrogen protection, backflow is heated with stirring to, reaction temperature is controlled at 200 DEG C,
And the water steamed is collected, treat that water is almost collected and finish and (about react 1h).0.4mol adipic acids are it is possible to additionally incorporate into system, continue to stir
Mix and be heated to flowing back, reaction temperature is controlled at 220 DEG C, is collected the water steamed, is almost collected to water and finish and (about react 1.5h).So
Afterwards, the system is passed through into the purifying of vacuum volatilization in the condition polycondensation about 5h that temperature is 180-200 DEG C, absolute pressure is 100Pa
Method obtains 120g yellowish aliphatic-aromatic copolyester DP1, and its weight average molecular weight is 53000, and molecular weight distribution refers to
Number is 1.88, and in copolyesters DP1, the content of butyl titanate is 0.041 weight %,
Embodiment 1
The present embodiment is used to illustrate aliphatic-aromatic-PLA copolyesters product of the present invention and preparation method thereof.
80g L- lactide monomers (LLA) and 30g aliphatic-aromatic copolyesters P1 is added separately in reaction vessel
(on the basis of the total amount of aliphatic-aromatic copolymer p 1 and lactide monomer, the content of butyl titanate is 0.016 weight %,
The content of lanthanum acetylacetone is 0.011 weight %), 5h will be purged with high pure nitrogen after being well mixed, under nitrogen atmosphere will be anti-
Answer container to be placed at 170 DEG C after reaction 5h, cooling, with chloroform diluted mixture, and precipitated in absolute methanol, gained
Sediment be aliphatic-aromatic-PLA copolyesters product A1 (97g, wherein, the content of titanium is 0.0022 weight %, lanthanum
Content be 0.0036 weight %), its copolyesters/lactide weight ratio, weight average molecular weight, molecular weight distributing index, stretching are strong
Degree and fracture elongation rate are as shown in table 1.
Embodiment 2
The present embodiment is used to illustrate aliphatic-aromatic-PLA copolyesters product of the present invention and preparation method thereof.
80g L- lactide monomers (LLA) and 80g aliphatic-aromatic copolyesters P1 is added separately in reaction vessel
(on the basis of the total amount of aliphatic-aromatic copolymer p 1 and lactide monomer, the content of butyl titanate is 0.03 weight %,
The content of lanthanum acetylacetone is 0.025 weight %), 5h will be purged with high pure nitrogen after being well mixed, under nitrogen atmosphere will be anti-
Answer container to be placed at 160 DEG C after reaction 5h, cooling, with chloroform diluted mixture, and precipitated in absolute methanol, gained
Sediment be aliphatic-aromatic-PLA copolyesters product A2 (100g, wherein, the content of titanium is 0.0021 weight %,
The content of lanthanum is 0.0047 weight %), its copolyesters/lactide weight ratio, weight average molecular weight, molecular weight distributing index, stretching
Intensity and fracture elongation rate are as shown in table 1.
Embodiment 3
The present embodiment is used to illustrate aliphatic-aromatic-PLA copolyesters product of the present invention and preparation method thereof.
According to the method described in embodiment 1, no institute is to replace P1 using 30g aliphatic-aromatic copolyesters P2
(on the basis of the total amount of aliphatic-aromatic copolymer p 2 and lactide monomer, the content of butyl titanate is 0.011 weight %,
The content of Lanthanum Stearate is 0.0068 weight %), obtain aliphatic-aromatic-PLA copolyesters product A3 (95g, wherein,
The content of titanium is 0.0016 weight %, and the content of lanthanum is 0.0025 weight %), its copolyesters/lactide weight ratio, Weight-average molecular
Amount, molecular weight distributing index, tensile strength and fracture elongation rate are as shown in table 1.
Embodiment 4
According to the method described in embodiment 3, except that, aliphatic-aromatic copolyester P2 dosage is 80g (fat
On the basis of the total amount of fat race-aromatic copolymer P2 and lactide monomer, the content of butyl titanate is 0.02 weight %, stearic
The content of sour lanthanum is 0.012 weight %), obtain aliphatic-aromatic-PLA copolyesters product A4 (105g, wherein, titanium
Content is 0.0028 weight %, and the content of lanthanum is 0.0045 weight %), its copolyesters/lactide weight ratio, weight average molecular weight,
Molecular weight distributing index, tensile strength and fracture elongation rate are as shown in table 1.
Embodiment 5
According to the method described in embodiment 1, institute is no to be, using 80g D- lactide monomers and 30g aliphatic-virtue
(on the basis of the total amount of aliphatic-aromatic copolymer p 3 and lactide monomer, the content of titanium dioxide is fragrant race's copolyesters P3
0.011 weight %, the content of lanthanum chloride is 0.014 weight %), obtain aliphatic-aromatic-PLA copolyesters product A5
(90g, wherein, the content of titanium is 0.0015 weight %, and the content of lanthanum is 0.0054 weight %), its copolyesters/lactide weight
Than, weight average molecular weight, molecular weight distributing index, tensile strength and fracture elongation rate it is as shown in table 1.
Comparative example 1
According to the method described in embodiment 1, except that, P1 is replaced using 30g aliphatic-aromatic copolyesters DP1
It is added in reactor that (on the basis of the total amount of aliphatic-aromatic copolymer DP1 and lactide monomer, butyl titanate contains
Measure as 0.011 weight %), obtain aliphatic-aromatic-PLA copolyesters product DA1 (75g, wherein, the content of titanium is
0.0037 weight %), its copolyesters/lactide weight ratio, weight average molecular weight, molecular weight distributing index, tensile strength and fracture
Elongation rate is as shown in table 1.
Comparative example 2
According to the method described in comparative example 1, except that, after adding 100mg stannous octoate into reactor
Start to react, obtain aliphatic-aromatic-PLA copolyesters product DA2 (103g, wherein, the content of titanium is 0.0015 weight
% is measured, the content of tin is 0.02 weight %), its copolyesters/lactide weight ratio, weight average molecular weight, molecular weight distributing index, drawing
Stretch intensity and fracture elongation rate is as shown in table 1.
Comparative example 3
According to the method described in embodiment 1, except that, the further stannous octoate for adding 80mg ability into reactor
Start to react, obtain aliphatic-aromatic-PLA copolyesters product DA3 (99g, wherein, the content of titanium is 0.0022 weight
% is measured, the content of lanthanum is 0.0036 weight %, and the content of tin is 0.017 weight %), its copolyesters/lactide weight ratio, weight are equal
Molecular weight, molecular weight distributing index, tensile strength and fracture elongation rate are as shown in table 1.
Comparative example 4
The butyl titanate of 80g L- lactides and 80mg is added in reactor and is well mixed.Then nitrogen is used
Reactor is purged 5 hours, and reaction bulb is placed into 190 DEG C of oil bath under nitrogen atmosphere, it is cold after reacting 1.5 hours
But, the product obtained after reaction is dissolved with chloroform, and precipitated in absolute methanol, gained sediment be aliphatic-
Aromatic series-PLA copolyesters product DA4 (58g, wherein, the content of titanium is 0.02 weight %), its copolyesters/lactide weight
Than, weight average molecular weight, molecular weight distributing index, tensile strength and fracture elongation rate it is as shown in table 1.
Table 1
Note：DA1 and DA4 can not carry out tensile strength and the measure of elongation at break because sample is too crisp.
The aliphatic-aromatic relative to comparative example 1-PLA copolyesters product is can be seen that by the data of table 1
DA1, because embodiments of the invention produce using rare earth-Titanium series catalyst the product of aliphatic-aromatic copolymer,
So that in the preparation of later aliphatic-aromatic-PLA copolyesters product, in the production of aliphatic-aromatic copolymer
The performance that the rare-earth metal catalyst remained in thing can help aliphatic-aromatic-PLA copolyesters product is more excellent；
Relative to comparative example 2, although comparative example 2 with the addition of in the preparation of later aliphatic-aromatic-PLA copolyesters product
Stannous octoate catalyst, but the addition of this partial catalyst does not only result in gained aliphatic-aromatic-PLA copolyesters production
The tenor of product greatly improves, prior, for the embodiment of the preparation method using the present invention, comparative example 2
The addition of middle stannous octoate catalyst does not bring larger to the performance of aliphatic-aromatic-PLA copolyesters product
Improve；Comparative example 3 equally with the addition of stannous octoate catalyst in the preparation of aliphatic-aromatic-PLA copolyesters product,
But catalyst especially addition not cause aliphatic-aromatic-PLA copolyesters product performance have it is larger
Improvement, thus it is speculated that its reason is probably that stannous octoate catalyst is more beneficial for aliphatic-aromatic-PLA copolyesters product
Well-regulated polymerization, be more likely to form block copolymer, without obtain the present invention random aliphatic-aromatic-
PLA copolyesters product, although the product in the case of the intensity maintained like, also has very excellent tensile property,
But its elongation at break is poor；Comparative example 4 is only the preparation process of conventional PLA, by contrast as can be seen that the present invention
The aliphatic-aromatic of gained-PLA copolyesters resultant metal constituent content is low, but performance is but more superior.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (20)
1. the preparation method of a kind of aliphatic-aromatic-PLA copolyesters product, it is characterised in that this method includes following
Step：
(1) in the presence of Titanium series catalyst, component a, component b and component c are subjected to esterification；
(2) under vacuum, the esterification reaction mixture of gained in step (1) is subjected to pre-polymerization；
(3) in the presence of rare-earth metal catalyst, the prepolymerization reaction mixture of gained in step (2) is subjected to polycondensation reaction,
The product of aliphatic-aromatic copolymer is obtained, wherein, in the product of the aliphatic-aromatic copolymer, the titanium system
The content of catalyst is 0.04-0.08 weight %, and the content of the rare-earth metal catalyst is 0.022-0.1 weight %；
(4) product of the aliphatic-aromatic copolymer obtained by step (3) and lactide monomer are subjected to copolyreaction, wherein,
The product of the aliphatic-aromatic copolymer and the dosage of lactide monomer cause：Using the gross weight of lactide monomer as base
Standard, the content of the Titanium series catalyst is 0.017-0.08 weight %, and the content of the rare-earth metal catalyst is 0.0033-
0.1 weight %；
Wherein, the component a is C8-C20Aromatic acid, the C8-C20Aromatic acid acid anhydrides and the C8-
C20Aromatic acid ester in one or more；The component b is C2-C10Aliphatic dihydroxy alcohol and/or C3-C10's
Cycloaliphatic diols；The component c is C2-C20Aliphatic dibasic acid, 1,4- cyclohexane diacids, 1,2,4,5- hexamethylene tetracids
One or more in dianhydride and norbornane diacid.
2. preparation method according to claim 1, wherein, in step (4), the production of the aliphatic-aromatic copolymer
The dosage of thing and lactide monomer causes：On the basis of the gross weight of lactide monomer, the content of the Titanium series catalyst is
0.02-0.073 weight %, the content of the rare-earth metal catalyst is 0.01-0.095 weight %.
3. preparation method according to claim 1, wherein, the dosage of the Titanium series catalyst in step (1) and step (3)
The mol ratio of the dosage of rare-earth metal catalyst in prepolymerization reaction is 1：0.4-1.
4. preparation method according to claim 1, wherein, the Titanium series catalyst be butyl titanate, titanium isopropoxide,
One or more in titanium dioxide and titanium tetrachloride；The rare-earth metal catalyst is lanthanum acetylacetone, lanthanum chloride, isopropyl oxygen
One or more in base neodymium, 2,6- dibutyl -4- methylenedioxy phenoxies neodymium and Lanthanum Stearate.
5. preparation method according to claim 1, wherein, the component a is M-phthalic acid, terephthalic acid (TPA), adjacent benzene
Dioctyl phthalate, 2,6- naphthalenedicarboxylic acids, 1,5- naphthalenedicarboxylic acids, 2,7- naphthalenedicarboxylic acids, 4,4 '-biphenyl dicarboxylic acid and 3,4 '-biphenyl diformazan
One or more in acid；The component b is ethylene glycol, diethylene glycol (DEG), propane diols, butanediol, pentanediol, hexylene glycol, hexamethylene
One or more in glycol and norbornane dimethanol；The component c is succinic acid, succinic anhydride, adipic acid, adipic acid
Acid anhydride, azelaic acid, decanedioic acid, dodecanedioic acid, 1,4- cyclohexane diacids, 1,2,4,5- hexamethylenes tetracarboxylic dianhydride and norbornane two
One or more in acid.
6. preparation method according to claim 5, wherein, the component a is terephthalic acid (TPA).
7. preparation method according to claim 5, wherein, the component b is butanediol.
8. preparation method according to claim 5, wherein, the component c is adipic acid.
9. preparation method according to claim 1, wherein, the component a, component b and component c mol ratio are 1：(2-
5)：(0.8-3).
10. preparation method according to claim 9, wherein, the component a, component b and component c mol ratio are 1：(2-
4.5)：(0.8-2.5).
11. preparation method according to claim 1, wherein, using the component a, component b and component c integral molar quantity as
Benchmark, in step (1), the dosage of the Titanium series catalyst is 0.01-0.04mol%.
12. preparation method according to claim 11, wherein, using the component a, component b and component c integral molar quantity as
Benchmark, in step (1), the dosage of the Titanium series catalyst is 0.016-0.029mol%.
13. preparation method according to claim 1, wherein, using the component a, component b and component c integral molar quantity as
Benchmark, in step (3), the dosage of the rare-earth metal catalyst is 0.005-0.03mol%.
14. preparation method according to claim 13, wherein, using the component a, component b and component c integral molar quantity as
Benchmark, in step (3), the dosage of the rare-earth metal catalyst is 0.008-0.015mol%.
15. preparation method according to claim 1, wherein, the product of the aliphatic-aromatic copolymer is divided equally again
Son amount is 3000-40000, molecular weight distribution index 1.2-2.5.
16. preparation method according to claim 1, wherein, in step (1), the condition of the esterification includes：Reaction
Temperature is 150-230 DEG C, reaction time 2-7h；In step (2), the condition of the pre-polymerization includes：Absolute pressure be 500Pa with
Under, reaction temperature is 200-250 DEG C, reaction time 1-6h；In step (3), the condition of the polycondensation reaction includes：Absolute pressure
Power is below 400Pa, and reaction temperature is 220-250 DEG C, reaction time 1-5h；In step (4), the condition of the copolyreaction
Including：Reaction temperature is 150-190 DEG C, reaction time 2-5h.
17. preparation method according to claim 16, wherein, in step (1), the esterification includes：First by component a
The first esterification is carried out with component b, then the material after the first esterification and component c are subjected to the second esterification；Wherein,
The condition of first esterification includes：Reaction temperature is 150-230 DEG C, reaction time 1-3h；Second esterification is anti-
The condition answered includes：Reaction temperature is 180-220 DEG C, reaction time 1-4h.
18. aliphatic-aromatic-PLA made from the preparation method in a kind of 1-17 as claim described in any one is common
Polyester product.
19. aliphatic-aromatic according to claim 18-PLA copolyesters product, wherein, the aliphatic-virtue
Metal element content in fragrant race-PLA copolyesters product is below 0.02 weight %.
20. aliphatic-aromatic according to claim 19-PLA copolyesters product, wherein, the aliphatic-virtue
Metal element content in fragrant race-PLA copolyesters product is 0.002-0.015 weight %.
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| CN109942396A (en) * | 2019-04-12 | 2019-06-28 | 江苏温塑实业有限公司 | The Preparation Method of lanthanum acetylacetone |
| CN110283063B (en) * | 2019-06-11 | 2020-06-16 | 中山华明泰科技股份有限公司 | Preparation method and application of lanthanum acetylacetonate |
| CN114058158B (en) * | 2020-07-30 | 2023-08-15 | 中国石油化工股份有限公司 | Aliphatic aromatic copolyester foaming composition, aliphatic aromatic copolyester foaming sheet and preparation method thereof |
| CN115124702A (en) * | 2021-03-26 | 2022-09-30 | 华润化学材料科技股份有限公司 | Degradable aromatic-aliphatic copolyester material and preparation method and application thereof |
| CN113754871B (en) * | 2021-08-13 | 2023-06-13 | 浙江恒逸石化研究院有限公司 | Biodegradable block copolyesters based on lactide- (cycloaliphatic-co-aromatic) -lactide |
| 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 |
| CN115322527A (en) * | 2022-06-27 | 2022-11-11 | 广东春夏新材料科技股份有限公司 | Biodegradable polyester composite material and preparation method thereof |
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| CN103788600A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Polylactic acid-polyester composite material and preparation method thereof |
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