CN105585694A - Flexible aliphatic-aromatic-polylactic acid copolymer ester product and preparation method thereof - Google Patents
Flexible aliphatic-aromatic-polylactic acid copolymer ester product and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a flexible aliphatic-aromatic-polylactic acid copolymer ester product. In the method, by means of control on contents of a titanium-series catalyst and a rare earth metal catalyst, an aliphatic-aromatic copolymer product being low in rare earth/titanium-series catalyst content is produced; and then polymerization of the flexible aliphatic-aromatic-polylactic acid copolymer ester product is initiated through the aliphatic-aromatic copolymer product. The invention also provides the flexible aliphatic-aromatic-polylactic acid copolymer ester product prepared through the method. The flexible aliphatic-aromatic-polylactic acid copolymer ester product is low in metal content, has high use safety, is high in flexibility and overcomes a defect of brittleness of polylactic acid.
Description
Technical field
The present invention relates to a kind of pliable and tough aliphatic-aromatic-PLA copolyesters product and preparation method thereof.
Background technology
Well-known PLA is as a kind of Green Polymer Material, because it has biogenetic derivation,Therefore Efforts To Develop PLA industry can alleviate the pressure to petrochemical industry resource, and it is for alleviating temperatureChamber effect also has benifit. But poly-lactic acid material character is more crisp, toughness deficiency, therefore enters PLARow is toughness reinforcing is the important directions of improving PLA performance. Wherein, PLA being carried out to chain extension is to improve to gatherOne of method of lactic acid toughness. But most chain extender is all to contain isocyanates or epoxy one-tenthPoint, these compositions may produce poisonous and harmful substance in material degradation process, are unfavorable for materialLarge-scale application.
Copolymerization is a kind of chain extension method of very effective plasticizing polylactic acid. As patent applicationIn CN1911983A, mention, to carry out open loop poly-with any two kinds in lactide, glycolide or caprolactoneClose, obtain hydroxy-end capped oligomer; Again this hydroxy-end capped oligomer and linear polyester are carried out to melting poly-Close, just can obtain the degradable high polymer material for stent in shape memory pipe cavity. But this is specialIn profit application, the ring-opening polymerisation of preparing hydroxy-end capped oligomer need to adopt the containing metal of high level to urgeAgent, and carry out melt polymerization with linear polyester and need under vulcabond coupling agent, carry out, makeObtain the final polymer of gained and still there is higher tenor and diisocyanate content, and with oneFixed toxicity.
Visible, improve in the field of its fragility defect PLA being carried out to chain extension, conventionally there is metalThe consumption of catalyst is high, adopt the problem of poisonous vulcabond coupling agent, thereby makes changing of gainedProperty PLA is also with certain toxicity.
Summary of the invention
The object of the invention is to overcome and existingly need to add higher amount when PLA is carried out to copolymerization chain extensionContaining metal catalyst and/or vulcabond coupling agent etc. thereby the polydactyl acid that makes gained withThe defect of higher toxicity, provides a kind of containing metal coupling agent and that use lower content that do not adoptCatalyst carries out PLA to carry out a kind of aliphatic-aromatic-PLA copolyesters of copolymerization chain extension modificationThe preparation method of product and the aliphatic-aromatic-PLA copolyesters product making thereof.
Conventionally, adopt lactide polymerization to prepare PLA copolyesters, all need additionally to add again thirdThe catalyst that lactide ring-opening polymerisation is required, as the compound that contains the transition metal such as metallic zinc or tin class,Thereby make the metallic element of residual higher amount in prepared PLA copolyesters, to making of its productThere is larger impact with security. But the present inventor finds, if adopt of the present inventionEnd is that the aliphatic-aromatic copolymer of hydroxyl causes lactide copolymerization with it, utilize aliphatic-In the situation of the terminal hydroxyl of aromatic copolymer, can be at the rare earth-Titanium series catalyst of less consumptionUnder initiation, obtain the copolymer-modified a kind of poly-lactic acid products of aliphatic-aromatic, i.e. aliphatic-fragranceFamily-PLA copolyesters product. Adopt the rare earth-Titanium series catalyst of less consumption can obtain less goldBelong to the polydactyl acid product of content, and more make inventor unexpectedly, this polydactyl acid productAlso there is extraordinary pliability, overcome PLA fragility defect originally. Thereby complete thisBright.
Thus, the invention provides a kind of preparation side of aliphatic-aromatic-PLA copolyesters productMethod, the method comprises the following steps:
(1), under the existence of Titanium series catalyst, component a, components b and amount of component b are carried out to esterification anti-Should;
(2), under vacuum condition, the esterification reaction mixture of gained in step (1) is carried out to pre-polymerization;
(3), under the existence of rare-earth metal catalyst, the prepolymerization reaction of gained in step (2) is mixedThing carries out polycondensation reaction, obtains the product of aliphatic-aromatic copolymer, wherein, described aliphatic-In the product of aromatic copolymer, the content of described Titanium series catalyst is 0.04-0.08 % by weight, described inThe content of rare-earth metal catalyst is 0.022-0.1 % by weight;
(4) product and the lactide monomer of the aliphatic-aromatic copolymer of step (3) gained are enteredRow copolyreaction, wherein, the product of described aliphatic-aromatic copolymer and the consumption of lactide monomerMake: taking the gross weight of lactide monomer as benchmark, the content of described Titanium series catalyst is 0.017-0.08% by weight, the content of described rare-earth metal catalyst is 0.0033-0.1 % by weight;
Wherein, described component a is C8-C20Aromatic acid, described C8-C20Aromatic dicarboxylicAcid anhydrides and the described C of acid8-C20The ester of aromatic acid in one or more; Described components b isC2-C10Aliphatic dihydroxy alcohol and/or C3-C10Alicyclic dihydroxylic alcohols; Described amount of component b is C2-C20Aliphatic dibasic acid, C3-C10Alicyclic binary acid and their acid anhydrides in one or more.
The present invention also provides the prepared aliphatic-aromatic-PLA of said method copolyesters product.
By adopting method of the present invention, because the aliphatic-aromatic that step (1)-(3) make is total toIn the product of polymers, contain the rare earth-Titanium series catalyst of less consumption, and prepared aliphatic-fragranceFamily's copolymer has active terminal hydroxy group, so can be with adopting this to contain a small amount of rare earth-Titanium series catalystProduct and the lactide monomer of aliphatic-aromatic copolymer carry out copolyreaction, thereby lacking at thisUnder amount rare earth-Titanium series catalyst causes, utilizing the active terminal hydroxy group of aliphatic-aromatic copolymerUnder condition, obtain the copolymer-modified a kind of poly-lactic acid products of aliphatic-aromatic, i.e. aliphatic-fragranceFamily-PLA copolyesters product. This aliphatic-aromatic-PLA copolyesters product has lower goldBelong to content, thereby there is higher safety in utilization, and there is higher pliability, overcome poly-Lactic acid fragility defect originally.
Other features and advantages of the present invention are said the detailed description of the invention part subsequently in detailBright.
Detailed description of the invention
Below the specific embodiment of the present invention is elaborated. Should be understood that this placeThe detailed description of the invention of describing, only for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of aliphatic-aromatic-PLA copolyesters product, the methodComprise the following steps:
(1), under the existence of Titanium series catalyst, component a, components b and amount of component b are carried out to esterification anti-Should;
(2), under vacuum condition, the esterification reaction mixture of gained in step (1) is carried out to pre-polymerization;
(3), under the existence of rare-earth metal catalyst, the prepolymerization reaction of gained in step (2) is mixedThing carries out polycondensation reaction, obtains the product of aliphatic-aromatic copolymer, wherein, described aliphatic-In the product of aromatic copolymer, the content of described Titanium series catalyst is 0.04-0.08 % by weight, described inThe content of rare-earth metal catalyst is 0.022-0.1 % by weight;
(4) product and the lactide monomer of the aliphatic-aromatic copolymer of step (3) gained are enteredRow copolyreaction, wherein, the product of described aliphatic-aromatic copolymer and the consumption of lactide monomerMake: taking the gross weight of lactide monomer as benchmark, the content of described Titanium series catalyst is 0.017-0.08% by weight, the content of described rare-earth metal catalyst is 0.0033-0.1 % by weight;
Wherein, described component a is C8-C20Aromatic acid, described C8-C20Aromatic dicarboxylicAcid anhydrides and the described C of acid8-C20The ester of aromatic acid in one or more; Described components b isC2-C10Aliphatic dihydroxy alcohol and/or C3-C10Alicyclic dihydroxylic alcohols; Described amount of component b is C2-C20Aliphatic dibasic acid, C3-C10Alicyclic binary acid and their acid anhydrides in one or more.
According to the present invention, step (1)-(3) will make the product of aliphatic-aromatic copolymer, shouldIn product, contain a large amount of aliphatic-aromatic copolymers and a small amount of Titanium series catalyst and rare earth metal urgedAgent, it will be appreciated by those skilled in the art that for the product of aliphatic-aromatic copolymer be by aliphatic-Aromatic copolymer and catalyst composition. Under preferable case, in this product, described Titanium series catalystContent is preferably 0.04-0.073 % by weight, more preferably 0.05-0.073 % by weight. Preferably, described inThe content of rare-earth metal catalyst is 0.025-0.095 % by weight, more preferably 0.028-0.055 % by weight.
According to the present invention, under preferable case, the consumption of the Titanium series catalyst in step (1) and step (3)Prepolymerization reaction in the mol ratio of consumption of rare-earth metal catalyst be 1:0.4-1, more preferably 1: 05-1。
Wherein, the construction unit of described aliphatic-aromatic copolymer has structure shown in formula (1):
Formula (1)
Wherein, Ar is the group with phenyl ring, naphthalene nucleus or anthracene nucleus; M is preferably the integer of 1-20; nBe preferably the integer of 1-16; T is preferably the integer of 1-20; X can be the integer of 1-100, is preferablyThe integer of 15-60; Y can be the integer of 1-100, is preferably the integer of 15-60.
Under preferable case, Ar is following aryl:
Wherein, R1、R2、R3、R4、R5And R6Be independently of one another hydrogen, C1-C4 alkyl, F,Cl、-NO2,-CN or-OR7, wherein, R7For the alkyl of C1-C4.
In most preferred situation, Ar isWherein, R1And R2Same as above.
According to the present invention, in order to obtain the better transparency and flexility, under preferable case, described inThe weight average molecular weight of aliphatic-aromatic copolymer is 3000-40000, and molecular weight distribution coefficient is1.2-2.5. More preferably, the weight average molecular weight of described aliphatic-aromatic copolymer is6000-35000, molecular weight distribution coefficient is 1.4-2.2.
According to the present invention, in order to obtain the more good aliphatic-fragrance of flexility and degradation propertyFamily's copolymer, under preferable case, is M-phthalic acid, terephthalic acid (TPA), adjacent benzene two at described component aFormic acid, NDA, 1,5-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4 '-biphenyl dicarboxylic acid and 3,4 '-One or more in biphenyl dicarboxylic acid, more preferably terephthalic acid (TPA), M-phthalic acid and adjacent benzene twoOne or more in formic acid, are further preferably terephthalic acid (TPA).
Under preferable case, described components b is for being selected from ethylene glycol, diethylene glycol (DEG), propane diols, butanediol, pentaOne or more in glycol, hexylene glycol, cyclohexane diol and norbornane dimethanol, more preferablyOne or more in butanediol, hexylene glycol and cyclohexane diol, are further preferably butanediol.
Under preferable case, described amount of component b is succinic acid, succinic anhydride, adipic acid, adipic anhydride, the ninth of the ten Heavenly StemsDiacid, decanedioic acid, dodecanedioic acid, Isosorbide-5-Nitrae-cyclohexane diacid, 1,2,4,5-cyclohexane tetracarboxylic dianhydride and fallingOne or more in bornylane diacid, more preferably in succinic acid, adipic acid and Isosorbide-5-Nitrae-cyclohexane diacidOne or more, be further preferably adipic acid.
According to the present invention, although component a, components b and amount of component b are carried out to the anti-of step (1)-(3)Should obtain the product of described aliphatic-aromatic copolymer, in order to make component a, components b and groupDivide c to react more abundant and obtain the aliphatic-aromatic copolymer with biodegradability, preferablyIn situation, the mol ratio of described component a, components b and amount of component b is 1:(2-5): (0.8-3),More preferably 1:(2-4.5): (0.8-2.5), be further preferably 1:(2-4.4): (1-1.5).
According to the present invention, the consumption of described Titanium series catalyst is not particularly limited, as long as canThe carrying out of the described esterification in catalytic step (1), and promote aliphatic-aromatic copolymer and thirdLactide monomers copolymerization, but in order there to be enough amounts to meet the carrying out of described esterification, andPromote aliphatic-aromatic copolymer and lactide monomer copolymerization, can not give again aliphatic-aromatic copolymerizationIn the copolymer-modified poly-lactic acid products of the aliphatic-aromatic of thing and lactide monomer copolymerization, introduce too muchMetal element content, under preferable case, with the integral molar quantity of described component a, components b and amount of component bFor benchmark, in step (1), the consumption of described Titanium series catalyst is 0.01-0.04mol%, more preferably0.016-0.029mol％。
According to the present invention, in like manner, in order there to be enough amounts to meet polycondensation reaction described in step (3)Carrying out, and promote aliphatic-aromatic copolymer and lactide monomer copolymerization, can not give again aliphatic-The copolymer-modified poly-lactic acid products of aliphatic-aromatic of aromatic copolymer and lactide monomer copolymerizationThe metal element content that middle introduction is too much, under preferable case, with described component a, components b and amount of component bIntegral molar quantity be benchmark, the consumption of described rare-earth metal catalyst is 0.005-0.03mol%, more preferablyFor 0.008-0.015mol%.
According to the present invention, under preferable case, described Titanium series catalyst is butyl titanate, isopropoxyOne or more in titanium, titanium dioxide and titanium tetrachloride, more preferably butyl titanate, isopropyl oxygenOne or more in base titanium and titanium dioxide. Described Titanium series catalyst can be commercially available product, also can lead toCrossing conventional method makes.
According to the present invention, under preferable case, described rare-earth metal catalyst is acetylacetone,2,4-pentanedione lanthanum, anhydrousLanthanum chloride, isopropoxy neodymium, 2, the one in 6-dibutyl-4-methylenedioxy phenoxy neodymium and Lanthanum Stearate or manyKind, more preferably one or more in acetylacetone,2,4-pentanedione lanthanum, isopropoxy neodymium and Lanthanum Stearate. DescribedRare-earth metal catalyst can be commercially available product, also can make by conventional method, for example, pass through document“InorganicChemistry1970,9,2505,J.Chem.Soc.Chem.Commun.1983,1499 " method of recording in makes.
According to the present invention, under preferable case, the condition of described esterification comprises: reaction temperature is150-230 DEG C, the reaction time is 2-7h. More preferably in situation, the esterification in step (1) comprises:First component a and components b are carried out to the first esterification, then by the material after the first esterification and componentC carries out the second esterification. Wherein, under preferable case, the condition of described the first esterification comprises:Reaction temperature is 150-230 DEG C, and the reaction time is 1-3h. The condition of described the second esterification comprises:Reaction temperature is 180-220 DEG C, and the reaction time is 1-4h. More preferably, described the first esterificationCondition comprises: reaction temperature is 180-200 DEG C, and the reaction time is 2-3h. Described the second esterificationCondition comprises: reaction temperature is 200-220 DEG C, and the reaction time is 2-4h.
According to the present invention, under preferable case, in step (2), the condition of described pre-polymerization comprises: definitelyPressure is below 500Pa, and reaction temperature is 200-250 DEG C, and the reaction time is 1-6h. More preferably,The condition of described pre-polymerization comprises: absolute pressure is below 400Pa, and reaction temperature is 200-240 DEG C, anti-Between seasonable, be 1-3h.
Under preferable case, in step (3), the condition of described polycondensation reaction comprises: under absolute pressureBelow 400Pa, reaction temperature is 220-250 DEG C, and the reaction time is 1-5h. More preferably, described contractingThe condition of poly-reaction comprises: absolute pressure is below 400Pa, and reaction temperature is 220-240 DEG C, reactionTime is 1-2h.
According to the present invention, under preferable case, the reaction of above-mentioned steps (1)-(3) is all in nitrogen protectionUnder carry out.
According to the present invention, dry by carry out vacuum volatilization through the product that above-mentioned steps (1)-(3) makeDry, remove unreacted monomer etc., thereby obtain the product of the aliphatic-aromatic copolymer in the present inventionThing, therefore, remains with step (1) in the present invention in the product of described aliphatic-aromatic copolymerThe catalyst adding in the course of reaction of-(3), i.e. Titanium series catalyst and rare-earth metal catalyst, and instituteState in the product of aliphatic-aromatic copolymer except Titanium series catalyst and rare-earth metal catalyst nearly allFor described aliphatic-aromatic copolymer. As above, it will be appreciated by those skilled in the art that as thisThe product of aliphatic-aromatic copolymer of invention be by Titanium series catalyst and rare-earth metal catalyst andAliphatic-aromatic copolymer composition.
According to the present invention, the product of the aliphatic-aromatic copolymer that above-mentioned steps (1)-(3) are madeThing carries out copolyreaction with lactide monomer in step (4), thereby can obtain fat of the present inventionFamily-aromatic series-PLA copolyesters product.
Wherein, because the product of aliphatic-aromatic copolymer carries a small amount of Titanium series catalyst and rareEarth metal catalyst, urges thereby the copolyreaction of the step of making (4) is actually in the titanium system of this partAgent and rare-earth metal catalyst carry out under existing, under preferable case, and described aliphatic-aromatic copolymerizationThe product of thing and the consumption of lactide monomer make: taking the gross weight of lactide monomer as benchmark, and described titaniumThe content of series catalysts is 0.02-0.073 % by weight, and the content of described rare-earth metal catalyst is0.01-0.095 % by weight.
In addition, the product of described aliphatic-aromatic copolymer and the consumption of described lactide monomer are upperState in scope and can realize object of the present invention. Further preferably, hand over described third of 100 weight portionsEster monomer is benchmark, and the consumption of the product of described aliphatic-aromatic copolymer is 15-110 weight portion,More preferably 17-100 weight portion, is further preferably 35-100 weight portion.
According to the present invention, under preferable case, in step (4), the condition of described copolyreaction comprises:Reaction temperature is 150-190 DEG C, and the reaction time is 2-5h. More preferably, the condition of described copolyreactionComprise: reaction temperature is 170-185 DEG C, the reaction time is 2.5-5h.
Wherein, under preferable case, described copolyreaction is carried out under nitrogen atmosphere, and first to reactionSystem just starts to carry out copolyreaction after passing into nitrogen 1-5h.
According to the present invention, under preferable case, after described polymerisation finishes, add retarder thinner to enterRow dilution, then add methyl alcohol to precipitate, to obtain aliphatic-aromatic-PLA copolyesters productPrecipitation. Described retarder thinner can be chloroform, carrene, oxolane and DMFIn one or more, be preferably one or more in chloroform, carrene and oxolane.
The present invention also provides by the prepared aliphatic-aromatic-PLA of said method copolyesters and has producedProduct.
Due to product and the lactide list of the aliphatic-aromatic copolymer in step (4) in the present inventionIn the copolyreaction that body carries out, do not add extraly catalyst, make the aliphatic-aromatic of gained-poly-In lactic acid copolyesters product, contain very small amount of metallic element. For example, described aliphatic-aromatic-poly-Metal element content in lactic acid copolyesters product is below 0.02 % by weight, is preferably 0.002-0.015% by weight, is further preferably 0.004-0.008 % by weight.
According to the present invention, the product of the aliphatic-aromatic copolymer in step (4) and lactide listThe copolyreaction that body carries out is a kind of random copolymerization, aliphatic-aromatic copolymer wherein itBetween, between aliphatic-aromatic copolymer and lactide monomer, between lactide monomer, can occurPolymerization, and the product of their polymerizations also can carry out ester exchange again, thus the fat of gained of the present inventionFamily-aromatic series-PLA copolyesters product is also a kind of through the copolymer-modified poly-breast of aliphatic-aromaticThe atactic polymer of acid.
And the aliphatic-aromatic-PLA copolyesters product that adopts method of the present invention to make, removesHave outside the advantage containing the metallic element of small amount with higher safety in utilization, more unexpectedlyFind, the aliphatic-aromatic-PLA copolyesters product making by method of the present invention also has non-Normal good pliability, has overcome PLA fragility defect originally preferably.
Below will describe the present invention by embodiment.
In following catalyst preparation example, preparation example, preparation comparative example, embodiment and comparative example,
Wherein, in aliphatic-aromatic-PLA copolyesters, PLA/copolyesters weight ratio is to pass through coreMagnetic resonance method is measured;
Weight average molecular weight and molecular weight distributing index are to adopt gel permeation chromatography (GPC) to measure,Wherein, taking oxolane as solvent, Waters-208 (band Waters2410RI detector,1.5mL/min flow velocity, 30 DEG C) to measure on instrument, molecular weight is with single linear polystyrene standards school that dispersesAccurate;
Hot strength and fracture tensile strength are to carry out according to the method for recording in GB/T1040.2-2006Measure.
Catalyst preparation example 1
10g lanthana dissolves with excessive hydrochloric acid, adds the NH of 0.5g after heating is concentrated4Cl, carefully heatingRemove excessive HCl, after the solid drying obtaining, study and add in quartzy sublimation pipe, vacuum sublimation instituteObtaining solid is lanthanum chloride.
Catalyst preparation example 2
Lanthanum chloride 9.37mmol is dissolved in the water of 50mL, then joins the acetyl containing 56.2mmolIn the aqueous solution of acetone, at room temperature stir, by add 2NKOH the aqueous solution adjust pH inProperty. Reactant mixture stirs, and filters, dry at 60 DEG C, vacuum, obtains acetylacetone,2,4-pentanedione lanthanum 4g.
Catalyst preparation example 3
Lanthanum chloride 9.37mmol is dissolved in the water of 50mL, then joins the tristearin containing 20mmolAcid sodium the aqueous solution in, at room temperature stir, by add 2NHCl the aqueous solution adjust pH inProperty. Reactant mixture stirs, and filters, dry at 60 DEG C, vacuum, obtains Lanthanum Stearate 11g.
Preparation example 1
By 2.2mol terephthalic acid (TPA), 5mol butanediol and 1.6mmol butyl titanate (purchased from BeijingChemical reagents corporation, chemical pure) join in reactor, and under nitrogen protection, be heated with stirring to backStream, reaction temperature is controlled at 180 DEG C, and collects the water that steams, treats that water almost collects complete (approximately reaction2h). In system, add in addition 2.5mol succinic acid, continue to be heated with stirring to backflow, reaction temperatureBe controlled at 200 DEG C, collect the water that steams, almost collect complete (approximately reacting 2h) to water. Then, willThis system is the about 1h of pre-polymerization under 230 DEG C, the absolute pressure condition that is 400Pa in temperature. Finally, to thisIn system, adding 0.85mmol acetylacetone,2,4-pentanedione lanthanum, is that 230 DEG C, absolute pressure remain on 200Pa in temperatureUnder following condition, the about 1h of polycondensation, obtains white aliphatic-fragrance of 750g by vacuumizing devolatilizationThe copolyesters P1 of family, its weight average molecular weight is 10000, molecular weight distributing index is 2.2, and this copolymerizationIn ester P1, the content of butyl titanate is 0.06 % by weight, and the content of acetylacetone,2,4-pentanedione lanthanum is 0.041 weightAmount %.
Preparation example 2
2.2mol terephthalic acid (TPA), 5mol butanediol and 1.6mmol butyl titanate are joined to reactionIn device, and under nitrogen protection, be heated with stirring to backflow, reaction temperature is controlled at 200 DEG C, and collectsThe water steaming, treats that water almost collects complete (approximately reacting 2h). In system, add in addition 2.5mol fourthDiacid, continues to be heated with stirring to backflow, and reaction temperature is controlled at 220 DEG C, collects the water steaming, to waterAlmost collect complete (approximately reacting 2h). Then be, that 240 DEG C, absolute pressure are by this system in temperatureThe about 1h of pre-polymerization under the condition of 400Pa. Finally, in this system, add 0.85mmol Lanthanum Stearate,Temperature is that 240 DEG C, absolute pressure remain under the condition below 200Pa, and the about 1.5h of polycondensation, by moltenUnder melting, vacuumize the white aliphatic-aromatic copolyester P2 that devolatilization obtains 700g, its weight average molecular weightBe 31000, molecular weight distributing index is 1.67, and in this copolyesters P2, the containing of butyl titanateAmount is 0.041 % by weight, and the content of Lanthanum Stearate is 0.025 % by weight.
Preparation example 3
By 0.3mol terephthalic acid (TPA), 1.35mol butanediol and 0.7mmol titanium dioxide (purchased from BeijingChemical reagents corporation, chemical pure) join in reactor, and under nitrogen protection, be heated with stirring to backStream, reaction temperature is controlled at 180 DEG C, and collects the water that steams, treats that water almost collects complete (approximately reaction2h). In system, add in addition 0.75mol adipic acid, continue to be heated with stirring to backflow, reaction temperatureBe controlled at 200 DEG C, collect the water that steams, almost collect complete (approximately reacting 2h) to water. Then, willThis system is the about 1h of pre-polymerization under 180 DEG C, the absolute pressure condition that is 500Pa in temperature. Finally, to thisIn system, adding 0.35mmol anhydrous lanthanum chloride, is that 220 DEG C, absolute pressure remain on 150Pa in temperatureUnder following condition, the about 1h of polycondensation, obtain by vacuumizing devolatilization the yellowish aliphatic of 230g-Aromatic copolyester P3, its weight average molecular weight is 35000, molecular weight distributing index is 1.95, and shouldIn copolyesters P3, the content of titanium dioxide is 0.041 % by weight, and the content of lanthanum chloride is 0.053 weightAmount %.
Preparation comparative example 1
By 0.4mol terephthalic acid (TPA), 0.96mol butanediol and 0.5mmol butyl titanate (purchased from northCapital chemical reagents corporation, chemical pure) join in reactor, and under nitrogen protection, be heated with stirring toReflux, reaction temperature is controlled at 200 DEG C, and collects the water that steams, treats that water almost collects complete (approximately anti-Answer 1h). In system, add in addition 0.4mol adipic acid, continue to be heated with stirring to backflow, reaction temperatureDegree is controlled at 220 DEG C, collects the water that steams, almost collects complete (approximately reacting 1.5h) to water. Then,Be the about 5h of condition polycondensation that 180-200 DEG C, absolute pressure are 100Pa by this system in temperature, by veryThe purification process of empty devolatilization obtains the yellowish aliphatic-aromatic copolyester DP1 of 120g, its weight averageMolecular weight is 53000, and molecular weight distributing index is 1.88, and in this copolyesters DP1, metatitanic acid four fourthsThe content of ester is 0.041 % by weight,
Embodiment 1
The present embodiment is used for illustrating aliphatic-aromatic-PLA copolyesters product of the present invention and preparation thereofMethod.
L-lactide monomer (LLA) and the 30g aliphatic-aromatic copolyester P1 of 80g add respectivelyIn reaction vessel, (aliphatic-aromatic copolymer p 1 is benchmark with the total amount of lactide monomer, metatitanic acidThe content of four butyl esters is 0.016 % by weight, and the content of acetylacetone,2,4-pentanedione lanthanum is 0.011 % by weight), mix allAfter even, will purge 5h with high pure nitrogen, and under nitrogen atmosphere, reaction vessel will be placed at 170 DEG C and react 5After h, cooling, with chloroform dilution mixture, and precipitate in absolute methanol, gained sediment isFor aliphatic-aromatic-PLA copolyesters product A 1, (97g, wherein, the content of titanium is 0.0022 weightAmount %, the content of lanthanum is 0.0036 % by weight), its lactide/copolyesters weight ratio, weight average molecular weight,Molecular weight distributing index, hot strength and fracture elongation rate are as shown in table 1.
Embodiment 2
The present embodiment is used for illustrating aliphatic-aromatic-PLA copolyesters product of the present invention and preparation thereofMethod.
L-lactide monomer (LLA) and the 80g aliphatic-aromatic copolyester P1 of 80g add respectivelyIn reaction vessel, (aliphatic-aromatic copolymer p 1 is benchmark with the total amount of lactide monomer, metatitanic acidThe content of four butyl esters is 0.03 % by weight, and the content of acetylacetone,2,4-pentanedione lanthanum is 0.025 % by weight), mix allAfter even, will purge 5h with high pure nitrogen, and under nitrogen atmosphere, reaction vessel will be placed at 160 DEG C and react 5After h, cooling, with chloroform dilution mixture, and precipitate in absolute methanol, gained sediment isFor aliphatic-aromatic-PLA copolyesters product A 2, (100g, wherein, the content of titanium is 0.0021% by weight, the content of lanthanum is 0.0047 % by weight), its lactide/copolyesters weight ratio, weight average moleculeAmount, molecular weight distributing index, hot strength and fracture elongation rate are as shown in table 1.
Embodiment 3
The present embodiment is used for illustrating aliphatic-aromatic-PLA copolyesters product of the present invention and preparation thereofMethod.
According to the method described in embodiment 1, institute is no, adopts the copolymerization of 30g aliphatic-aromaticEster P2 replaces P1, and (aliphatic-aromatic copolymer p 2 is benchmark with the total amount of lactide monomer, metatitanic acidThe content of four butyl esters is 0.011 % by weight, and the content of Lanthanum Stearate is 0.0068 % by weight), obtain fat(95g, wherein, the content of titanium is 0.0016 weight to fat family-aromatic series-PLA copolyesters product A 3Amount %, the content of lanthanum is 0.0025 % by weight), its lactide/copolyesters weight ratio, weight average molecular weight,Molecular weight distributing index, hot strength and fracture elongation rate are as shown in table 1.
Embodiment 4
According to the method described in embodiment 3, difference is, the use of aliphatic-aromatic copolyester P2For 80g, (aliphatic-aromatic copolymer p 2 is benchmark with the total amount of lactide monomer to amount, metatitanic acid four fourthsThe content of ester is 0.02 % by weight, and the content of Lanthanum Stearate is 0.012 % by weight), obtain aliphatic-(105g, wherein, the content of titanium is 0.0028 % by weight to aromatic series-PLA copolyesters product A 4, lanthanumContent be 0.0045 % by weight), its lactide/copolyesters weight ratio, weight average molecular weight, molecular weightProfile exponent, hot strength and fracture elongation rate are as shown in table 1.
Embodiment 5
According to the method described in embodiment 1, institute no, adopt 80g D-lactide monomer andThe 30g aliphatic-aromatic copolyester P3 (total amount of aliphatic-aromatic copolymer p 3 and lactide monomerFor benchmark, the content of titanium dioxide is 0.011 % by weight, and the content of lanthanum chloride is 0.014 % by weight),(90g, wherein, the content of titanium is 0.0015 to obtain aliphatic-aromatic-PLA copolyesters product A 5% by weight, the content of lanthanum is 0.0054 % by weight), its lactide/copolyesters weight ratio, weight average moleculeAmount, molecular weight distributing index, hot strength and fracture elongation rate are as shown in table 1.
Comparative example 1
According to the method described in embodiment 1, difference is to adopt the copolymerization of 30g aliphatic-aromaticEster DP1 replaces P1 to join (aliphatic-aromatic copolymer DP1 and lactide monomer in reactorTotal amount be benchmark, the content of butyl titanate is 0.011 % by weight), obtain aliphatic-aromatic-PLA copolyesters product DA1 (75g, wherein, the content of titanium is 0.0037 % by weight), its third friendshipEster/copolyesters weight ratio, weight average molecular weight, molecular weight distributing index, hot strength and fracture elongation rateAs shown in table 1.
Comparative example 2
According to the method described in comparative example 1, difference is, then adds the stannous octoate of 100mg to arriveAfter in reactor, just start reaction, obtain aliphatic-aromatic-PLA copolyesters product DA2(103g, wherein, the content of titanium is 0.0015 % by weight, the content of tin is 0.02 % by weight), it is third years oldLactide/copolyesters weight ratio, weight average molecular weight, molecular weight distributing index, hot strength and fracture are elongatedRate is as shown in table 1.
Comparative example 3
According to the method described in embodiment 1, difference is further to add the stannous octoate of 80mgTo just starting reaction in reactor, obtain aliphatic-aromatic-PLA copolyesters product DA3 (99g,Wherein, the content of titanium is 0.0022 % by weight, and the content of lanthanum is 0.0036 % by weight, and the content of tin is0.017 % by weight), its lactide/copolyesters weight ratio, weight average molecular weight, molecular weight distributing index,Hot strength and fracture elongation rate are as shown in table 1.
Comparative example 4
The butyl titanate of the L-lactide of 80g and 80mg is joined in reactor and mixed.Then with nitrogen, reactor is purged to 5 hours, and reaction bulb is placed into 190 DEG C under nitrogen atmosphereIn oil bath, react after 1.5 hours, cooling, the product that obtains after reaction is dissolved with chloroform, and in nothingIn water methanol, precipitate, gained sediment is aliphatic-aromatic-PLA copolyesters product DA4(58g, wherein, the content of titanium is 0.02 % by weight), its lactide/copolyesters weight ratio, weight average divideSub-amount, molecular weight distributing index, hot strength and fracture elongation rate are as shown in table 1.
Table 1
Note: DA1 and DA4, because sample is too crisp, cannot carry out the mensuration of hot strength and elongation at break.
Data by table 1 can be found out, common with respect to the aliphatic-aromatic-PLA of comparative example 1Polyester product DA1, due to embodiments of the invention employing is that rare earth-Titanium series catalyst is produced fatThe product of family-aromatic copolymer, makes at aliphatic-aromatic-PLA copolyesters product afterwardsIn preparation, rare-earth metal catalyst residual in the product of aliphatic-aromatic copolymer can helpThe performance of aliphatic-aromatic-PLA copolyesters product is more good; With respect to comparative example 2, althoughComparative example 2 has been added sad Asia in the preparation of aliphatic-aromatic-PLA copolyesters product afterwardsTin catalyst, but adding of this part catalyst not only causes gained aliphatic-aromatic-PLA commonThe tenor of polyester product improves greatly, prior, with respect to adopting preparation method's of the present inventionEmbodiment, in comparative example 2, stannous octoate catalyst adds not aliphatic-aromatic-poly-The performance of lactic acid copolyesters product is brought larger improvement; Comparative example 3 is equally at aliphatic-aromatic-poly-In the preparation of lactic acid copolyesters product, add stannous octoate catalyst, but the adding of catalyst especiallyDo not make the performance tool of aliphatic-aromatic-PLA copolyesters product have greatly improved, inferIts reason may be that stannous octoate catalyst is more conducive to aliphatic-aromatic-PLA copolyesters productWell-regulated polymerization, be more prone to form block copolymer, and can not obtain random fat of the present inventionFat family-aromatic series-PLA copolyesters product, although this product in the case of keeping same intensity,Also there is very good tensile property, but its elongation at break is poor; Comparative example 4 is only conventional gatheringThe preparation process of lactic acid, can find out the aliphatic-aromatic-PLA of gained of the present invention by contrastCopolyesters resultant metal constituent content is low, but performance is but more superior.
More than describe the preferred embodiment of the present invention in detail, still, the present invention is not limited to above-mentionedDetail in embodiment, within the scope of technical conceive of the present invention, can be to skill of the present inventionArt scheme is carried out multiple simple variant, and these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technology spy described in above-mentioned detailed description of the inventionLevy, in reconcilable situation, can combine by any suitable mode, for fear of notNecessary repetition, the present invention is to the explanation no longer separately of various possible combinations.
In addition, between various embodiment of the present invention, also can be combined, as long asIt is without prejudice to thought of the present invention, and it should be considered as content disclosed in this invention equally.
Claims (13)
1. a preparation method for aliphatic-aromatic-PLA copolyesters product, is characterized in that, shouldMethod comprises the following steps:
(1), under the existence of Titanium series catalyst, component a, components b and amount of component b are carried out to esterification anti-Should;
(2), under vacuum condition, the esterification reaction mixture of gained in step (1) is carried out to pre-polymerization;
(3), under the existence of rare-earth metal catalyst, the prepolymerization reaction of gained in step (2) is mixedThing carries out polycondensation reaction, obtains the product of aliphatic-aromatic copolymer, wherein, described aliphatic-In the product of aromatic copolymer, the content of described Titanium series catalyst is 0.04-0.08 % by weight, described inThe content of rare-earth metal catalyst is 0.022-0.1 % by weight;
(4) product and the lactide monomer of the aliphatic-aromatic copolymer of step (3) gained are enteredRow copolyreaction, wherein, the product of described aliphatic-aromatic copolymer and the consumption of lactide monomerMake: taking the gross weight of lactide monomer as benchmark, the content of described Titanium series catalyst is 0.017-0.08% by weight, the content of described rare-earth metal catalyst is 0.0033-0.1 % by weight;
Wherein, described component a is C8-C20Aromatic acid, described C8-C20Aromatic dicarboxylicAcid anhydrides and the described C of acid8-C20The ester of aromatic acid in one or more; Described components b isC2-C10Aliphatic dihydroxy alcohol and/or C3-C10Alicyclic dihydroxylic alcohols; Described amount of component b is C2-C20Aliphatic dibasic acid, C3-C10Alicyclic binary acid and their acid anhydrides in one or more.
2. method according to claim 1, wherein, in step (4), described aliphatic-FangThe product of fragrant family copolymer and the consumption of lactide monomer make: taking the gross weight of lactide monomer as baseStandard, the content of described Titanium series catalyst is 0.02-0.073 % by weight, the containing of described rare-earth metal catalystAmount is 0.01-0.095 % by weight.
3. method according to claim 1, wherein, the use of the Titanium series catalyst in step (1)The mol ratio of the consumption of the rare-earth metal catalyst in the prepolymerization reaction of amount and step (3) is 1:0.4-1.
4. method according to claim 1, wherein, described Titanium series catalyst is metatitanic acid four fourthsOne or more in ester, titanium isopropoxide, titanium dioxide and titanium tetrachloride; Described catalyzing of rare-earth metalAgent is acetylacetone,2,4-pentanedione lanthanum, lanthanum chloride, isopropoxy neodymium, 2,6-dibutyl-4-methylenedioxy phenoxy neodymium and stearic acidOne or more in lanthanum.
5. method according to claim 1, wherein, described component a is M-phthalic acid, rightPhthalic acid, phthalic acid, NDA, 1,5-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4 '-Biphenyl dicarboxylic acid and 3, one or more in 4 '-biphenyl dicarboxylic acid, are preferably terephthalic acid (TPA); Described groupPoint b be ethylene glycol, diethylene glycol (DEG), propane diols, butanediol, pentanediol, hexylene glycol, cyclohexane diol andOne or more in norbornane dimethanol, are preferably butanediol; Described amount of component b is succinic acid, fourthDicarboxylic anhydride, adipic acid, adipic anhydride, azelaic acid, decanedioic acid, dodecanedioic acid, Isosorbide-5-Nitrae-cyclohexane twoAcid, 1,2,4, one or more in 5-cyclohexane tetracarboxylic dianhydride and norbornane diacid, are preferably oneself twoAcid.
6. method according to claim 1, wherein, described component a, components b and amount of component bMol ratio be 1:(2-5): (0.8-3), be preferably 1:(2-4.5): (0.8-2.5).
7. method according to claim 1, wherein, with described component a, components b and amount of component bIntegral molar quantity be benchmark, in step (1), the consumption of described Titanium series catalyst is 0.01-0.04mol%,Be preferably 0.016-0.029mol%.
8. method according to claim 1, wherein, with described component a, components b and amount of component bIntegral molar quantity be benchmark, in step (3), the consumption of described rare-earth metal catalyst is0.005-0.03mol%, is preferably 0.008-0.015mol%.
9. method according to claim 1, wherein, the product of described aliphatic-aromatic copolymerThe weight average molecular weight of thing is 3000-40000, and molecular weight distribution coefficient is 1.2-2.5.
10. method according to claim 1, wherein, in step (1), described esterificationCondition comprise: reaction temperature is 15-230 DEG C, and the reaction time is 2-7h; In step (2), described inThe condition of pre-polymerization comprises: absolute pressure is below 500Pa, and reaction temperature is 200-250 DEG C, when reactionBetween be 1-6h; In step (3), the condition of described polycondensation reaction comprises: absolute pressure be 400Pa withUnder, reaction temperature is 220-250 DEG C, the reaction time is 1-5h; In step (4), described copolyreactionCondition comprise: reaction temperature is 150-190 DEG C, and the reaction time is 2-5h.
11. methods according to claim 10, wherein, in step (1), described esterificationComprise: first component a and components b are carried out to the first esterification, then by the material after the first esterificationCarry out the second esterification with amount of component b; Wherein, the condition of described the first esterification comprises: reaction temperatureDegree is 150-230 DEG C, and the reaction time is 1-3h; The condition of described the second esterification comprises: reaction temperatureDegree is 180-220 DEG C, and the reaction time is 1-4h.
12. 1 kinds of aliphatic-aromatics that made by the method described in any one in claim 1-11-PLA copolyesters product.
13. aliphatic-aromatic-PLA copolyesters product according to claim 12, itsIn, the metal element content in described aliphatic-aromatic-PLA copolyesters product is 0.02 % by weightBelow, be preferably 0.002-0.015 % by weight.
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| 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 |
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| CN114058158A (en) * | 2020-07-30 | 2022-02-18 | 中国石油化工股份有限公司 | Aliphatic and aromatic copolyester foaming composition, aliphatic and aromatic copolyester foaming plate and sheet and preparation method thereof |
| 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 |
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| CN113754871A (en) * | 2021-08-13 | 2021-12-07 | 浙江恒澜科技有限公司 | Biodegradable block copolyester based on lactide- (alicyclic-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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