CN102660008B - Aliphatic-aromatic copolyester and PLA (Poly Lactic Acid) block copolymer and production method and application thereof and composition containing block copolymer - Google Patents
Aliphatic-aromatic copolyester and PLA (Poly Lactic Acid) block copolymer and production method and application thereof and composition containing block copolymer Download PDFInfo
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- CN102660008B CN102660008B CN201210147450.4A CN201210147450A CN102660008B CN 102660008 B CN102660008 B CN 102660008B CN 201210147450 A CN201210147450 A CN 201210147450A CN 102660008 B CN102660008 B CN 102660008B
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Abstract
The invention discloses an aliphatic-aromatic copolyester and PLA (Poly Lactic Acid) block copolymer and a production method and an application thereof and a composition containing the block copolymer, which belong to the technical field of high molecular materials. The aliphatic-aromatic copolyester and PLA block copolymer consists of aliphatic-aromatic copolyester Q and a PLA block, and is taken as a biodegradable material; and the block copolymer can be prepared into a modified PLA material and a modified aliphatic-aromatic copolyester Q material. A product prepared with the method has wide production benefit and economic benefit.
Description
Technical field
The invention belongs to technical field of polymer materials, the composition that is specifically related to a kind of aliphatic-aromatic copolyester and PLA segmented copolymer, production method, purposes and contains this segmented copolymer.
Background technology
Along with the development of world economy, the mankind are increasing to the usage quantity of plastics, and the scope of use is also more and more extensive.Plastics have brought some problems of also having brought easily to the mankind simultaneously: 1, and the environmental pollution that a large amount of waste plastics, particularly plastics bag bring (white pollution).2, the finiteness of producing the raw material petroleum resources of plastics.
Bio-based degradable plastics poly(lactic acid) (PLA) can be biodegradable into CO under the condition of water oxygen appropriateness
2and H
2o, and the raw material of PLA comes from plant corn.The discovery of PLA and development have solved two problems that conventional plastic industry runs into, and can replace conventional plastic apply on a large scale in some industry and field.
PLA has good mechanical property as having higher intensity and modulus.Yet also have shortcoming, as poor toughness, resistance to impact shock is lower.Therefore will improve the mechanical property of PLA, expand its Application Areas, the toughness and the resistance to impact shock that improve PLA seem particularly important.
Biodegradable material aliphatic-aromatic copolyester Q has good toughness and elongation at break, is commonly used to improve with PLA blend toughness and the elongation at break of PLA.Yet its blend uncompatibility has hindered the performance of its resulting materials.
Summary of the invention
The problem existing for prior art, the object of the invention is to the technical scheme of the composition that design provides a kind of aliphatic-aromatic copolyester and PLA segmented copolymer, production method, purposes and contain this segmented copolymer.
Described a kind of aliphatic-aromatic copolyester and PLA segmented copolymer, is characterized in that consisting of aliphatic-aromatic copolyester Q and PLA block;
Described aliphatic-aromatic copolyester and PLA segmented copolymer are PLA-Q-PLA multipolymer;
Described aliphatic-aromatic copolyester Q is comprised of following polymerization single polymerization monomer:
A) one or more are selected from the compound of aliphatic dibasic acid, cycloalkyl diprotic acid or their ester, acid anhydrides, carboxylic acid halides;
B) one or more are selected from the compound of aromatic acid or its ester, acid anhydrides, carboxylic acid halides;
C) one or more are selected from the while with two compounds that are selected from the functional group of amino, sulfydryl or hydroxyl, or the compound of their derivative with epoxy group(ing), nitrogen heterocyclic or thia ring;
D) one or more are selected from the two keys of at least one carbon-to-carbon, carbon-oxygen, carbon-nitrogen or carbon-sulphur, the unsaturated acid of carbon-to-carbon or carbon-nitrogen triple bond or its ester, acid anhydrides, carboxylic acid halides; Or with the unsaturated alcohol of at least one carbon-to-carbon double bond or carbon-to-carbon triple bond or the compound of its epoxide;
Described aliphatic-aromatic copolyester is to be mixed by esterification, polycondensation by above-mentioned polymerization single polymerization monomer, then under the effect of initiator, makes polymerization single polymerization monomer D) on two keys and triple bond generation polymerization, grafting and/or linked reaction and make.
Described a kind of aliphatic-aromatic copolyester and PLA segmented copolymer, the number-average molecular weight that it is characterized in that described PLA-Q-PLA multipolymer is 10000～300000, and molecular weight distribution is 1.0～4.0, wherein the number-average molecular weight of aliphatic-aromatic copolyester Q is 2000～250000.
Described a kind of aliphatic-aromatic copolyester and the production method of PLA segmented copolymer, it is characterized in that with the ring-opening polymerization of aliphatic-aromatic copolyester Q initiation rac-Lactide, obtaining segmented copolymer PLA-Q-PLA under condition that catalyzer exists, described catalyzer is organo-metallic catalyst, be preferably organic bases earth metal compound, organo-transition metal compound, rare earth organic compounds, aluminium, germanium, tin, at least one in antimony organic compound or its mixture, stannous octoate more preferably, stannous octoate, zinc ethyl, aluminium isopropoxide, one or more mixtures in tetraisopropoxy titanium or ferric acetyl acetonade.
Described a kind of aliphatic-aromatic copolyester and the production method of PLA segmented copolymer, is characterized in that the consumption of described catalyzer is 0.01～5% of PLA-Q-PLA multipolymer total amount.
Described a kind of aliphatic-aromatic copolyester and the production method of PLA segmented copolymer, is characterized in that described aliphatic-aromatic copolyester Q and the consumption of rac-Lactide are 1～99:99～1, is preferably 20～80:80～20.
Described a kind of aliphatic-aromatic copolyester and the production method of PLA segmented copolymer, is characterized in that described temperature of reaction is at 80 ℃～300 ℃, and preferably temperature is 110 ℃～220 ℃.
Described a kind of aliphatic-aromatic copolyester and the production method of PLA segmented copolymer, is characterized in that the described reaction times is 0.5～48 hour, is preferably 6～24 hours.
The PLA material of described a kind of modification, is characterized in that comprising PLA and PLA-Q-PLA multipolymer.
The PLA material of described a kind of modification, is characterized in that the weight of described PLA-Q-PLA multipolymer accounts for 1～99.9% of blend total amount, is preferably 10%～50%.
The aliphatic-aromatic copolyester Q material of described a kind of modification, is characterized in that comprising aliphatic-aromatic copolyester Q and PLA-Q-PLA multipolymer.
The aliphatic-aromatic copolyester Q material of described a kind of modification, is characterized in that the weight of described PLA-Q-PLA multipolymer accounts for 1～99.9% of blend total amount, is preferably 10%～50%.
Described a kind of aliphatic-aromatic copolyester and PLA segmented copolymer, its application in biodegradable material.
Compared with prior art, the PLA-Q-PLA segmented copolymer that the present invention obtains by copolymerization, when applying as material separately, the advantage of comprehensive PLA and aliphatic-aromatic copolyester Q, had both had good intensity, also had good toughness and elongation at break.And its performance can regulate according to the aliphatic-aromatic copolyester Q chain length different from PLA.While using as properties-correcting agent, all there is good consistency with PLA and aliphatic-aromatic copolyester Q, can directly be used for PLA and aliphatic-aromatic copolyester Q to carry out modification, as macromole properties-correcting agent, there will not be migration, the shortcoming that small molecules properties-correcting agent has such as separate out.This product is complete biodegradable, during as material and properties-correcting agent use, can not be restricted.There is comparatively wide ecological benefits and economic benefit.
Embodiment
By example, further describe working of an invention mode below, but scope of the present invention is not only limited to these embodiment, these embodiment that give are only illustrative, unintelligible for being limitation of the present invention.The ordinary skill of this area is according to the content of invention, and some nonessential improvement that invention is made and adjustment still belong to protection scope of the present invention.
Embodiment mono-: by the dry aliphatic-aromatic copolyester Q of 5kg, in the dry also reactor that nitrogen replacement is crossed, be warming up to 100 degree, stirring velocity is adjusted to 20rpm, after the complete melting of aliphatic-aromatic copolyester Q, add 5kg rac-Lactide, and nitrogen replacement 3 times.Continue to stir after 30 minutes, add the sub-tin of octoate catalyst of mixture total weight amount 0.5%, react 24 hours.After reaction finishes, add phosphoric acid class stablizer, continue stirring reaction 30 minutes, then vacuumize devolatilization.Obtain segmented copolymer PLA-Q-PLA.
In embodiment mono-, catalyzer can adopt at least one or its mixture in organic bases earth metal compound, organo-transition metal compound, rare earth organic compounds, aluminium, germanium, tin, antimony organic compound, specifically can select one or more mixtures in stannous octoate, stannous octoate, zinc ethyl, aluminium isopropoxide, tetraisopropoxy titanium or ferric acetyl acetonade.It finally also can reach the technique effect identical with embodiment mono-.
Embodiment bis-: by the dry aliphatic-aromatic copolyester Q of 3kg, in the dry also reactor that nitrogen replacement is crossed, be warming up to 250 degree, stirring velocity is adjusted to 20rpm, after the complete melting of aliphatic-aromatic copolyester Q, add 7kg rac-Lactide, and nitrogen replacement 3 times.Continue to stir after 30 minutes, add the stannous octoate of mixture total weight amount 0.01%, react 3 hours.After reaction finishes, add phosphoric acid class stablizer, continue stirring reaction 30 minutes, then vacuumize devolatilization.Obtain segmented copolymer PLA-Q-PLA.
Embodiment tri-: by the dry aliphatic-aromatic copolyester Q of 7kg, in the dry also reactor that nitrogen replacement is crossed, be warming up to 200 degree, stirring velocity is adjusted to 20rpm, after the complete melting of aliphatic-aromatic copolyester Q, add 3kg rac-Lactide, and nitrogen replacement 3 times.Continue to stir after 30 minutes, add the zinc ethyl of mixture total weight amount 5%, react 12 hours.After reaction finishes, add phosphoric acid class stablizer, continue stirring reaction 30 minutes, then vacuumize devolatilization.Obtain segmented copolymer PLA-Q-PLA.
Embodiment tetra-: by the dry aliphatic-aromatic copolyester Q of 5kg, in the dry also reactor that nitrogen replacement is crossed, be warming up to 150 degree, stirring velocity is adjusted to 20rpm, after the complete melting of aliphatic-aromatic copolyester Q, add 5kg rac-Lactide, and nitrogen replacement 3 times.Continue to stir after 30 minutes, add the aluminium isopropoxide of mixture total weight amount 2%, react 6 hours.After reaction finishes, add phosphoric acid class stablizer, continue stirring reaction 30 minutes, then vacuumize devolatilization.Obtain segmented copolymer PLA-Q-PLA.
The segmented copolymer obtaining of above-described embodiment one-tetra-preparation is analyzed, be the results are shown in following table 1.
The character of the different feed ratio of table 1 and reaction conditions gained multipolymer.
The segmented copolymer obtaining of embodiment mono--tetra-preparation can be used as biodegradable material and uses.
The PLA-Q-PLA segmented copolymer of mentioned use in following example is described in embodiment mono-prepared by method condition, and feed ratio is 1:1.
Embodiment five: PLA9kg is mixed in high-speed mixer with PLA-Q-PLA1kg, then in twin screw extruder, be prepared into the PLA blend composition of plasticising toughening modifying.
Embodiment six: experimentation is identical with embodiment five, and PLA consumption is 4kg, and PLA-Q-PLA consumption is 1kg.
Embodiment seven: experimentation is identical with embodiment five, and PLA consumption is 3kg, and PLA-Q-PLA consumption is 2kg.
Embodiment eight: experimentation is identical with embodiment five, and PLA consumption is 2.5kg, and PLA-Q-PLA consumption is 2.5kg.
Embodiment nine: aliphatic-aromatic copolyester Q9kg is mixed in high-speed mixer with PLA-Q-PLA1kg, then in twin screw extruder, prepare the aliphatic-aromatic copolyester Q blend of enhancing modified.
Embodiment ten experimentations are identical with embodiment nine, and aliphatic-aromatic copolyester Q consumption is 4kg, and PLA-Q-PLA segmented copolymer consumption is 1kg.
Embodiment 11: experimentation is identical with embodiment nine, and aliphatic-aromatic copolyester Q consumption is 3kg, and PLA-Q-PLA segmented copolymer consumption is 2kg.
Embodiment 12: experimentation is identical with embodiment nine, and aliphatic-aromatic copolyester Q consumption is 2.5kg, and PLA-Q-PLA segmented copolymer consumption is 2.5kg.
Embodiment 13: by aliphatic-aromatic copolyester Q7kg, PLA3kg, after PLA-Q-PLA segmented copolymer 2kg mixes in high-speed mixer, with twin screw extruder blend granulation, obtain the aliphatic-aromatic copolyester Q/PLA blend alloy of capacity increasing modifying.
Embodiment 14: experimentation is identical with embodiment 13, and aliphatic-aromatic copolyester Q consumption is 6kg, and PLA consumption is 4kg, and PLA-Q-PLA segmented copolymer consumption is 2kg.
Embodiment 15: experimentation is identical with embodiment 13, and aliphatic-aromatic copolyester Q consumption is 5kg, and PLA consumption is 5kg, and PLA-Q-PLA segmented copolymer consumption is 2kg.
Embodiment 16: experimentation is identical with embodiment 13, and aliphatic-aromatic copolyester Q consumption is 5kg, and PLA consumption is 5kg, and PLA-Q-PLA segmented copolymer consumption is 1kg.
The blend alloy that above-mentioned embodiment is obtained is tested mechanical property after being prepared into batten, and result is as shown in the table:
The mechanical property of table 2 different mixture alloy.
N.B is not for by batten impact fracture.
In embodiment five～16, PLA-Q-PLA segmented copolymer adopts the middle PLA-Q-PLA segmented copolymer that embodiment bis-～tetra-makes, and its product finally obtaining also can reach the also identical technique effect in EXAMPLE Example five～16.
Aliphatic-aromatic copolyester Q in the present invention is currently available products, by Hangzhou Xinfu Pharmaceutical Co., Ltd., Zhejiang's production and sales; It is comprised of following polymerization single polymerization monomer: A) one or more are selected from the compound of aliphatic dibasic acid, cycloalkyl diprotic acid or their ester, acid anhydrides, carboxylic acid halides; B) one or more are selected from the compound of aromatic acid or its ester, acid anhydrides, carboxylic acid halides; C) one or more are selected from the while with two compounds that are selected from the functional group of amino, sulfydryl or hydroxyl, or the compound of their derivative with epoxy group(ing), nitrogen heterocyclic or thia ring; D) one or more are selected from the two keys of at least one carbon-to-carbon, carbon-oxygen, carbon-nitrogen or carbon-sulphur, the unsaturated acid of carbon-to-carbon or carbon-nitrogen triple bond or its ester, acid anhydrides, carboxylic acid halides; Or with the unsaturated alcohol of at least one carbon-to-carbon double bond or carbon-to-carbon triple bond or the compound of its epoxide; Described aliphatic-aromatic copolyester is to be mixed by esterification, polycondensation by above-mentioned polymerization single polymerization monomer, then under the effect of initiator, makes polymerization single polymerization monomer D) on two keys and triple bond generation polymerization, grafting and/or linked reaction and make.Its concrete production method can refer to the application documents that publication number is CN 101717493A.
Rac-Lactide is produced and is provided by Dutch PURAC company; Catalyzer, stablizer are provided by traditional Chinese medicinesization trial production.
In the invention process example, data determination method is as follows:
Gel permeation chromatography (GPC) is measured the molecular weight and molecualr weight distribution of polymkeric substance, take chloroform as solvent, at WATERS2695(band WATERS2414RI detector, 0.5ml/min, 30 ℃) detect on instrument.Take vinylbenzene as standard specimen calibration.
The employing GB/T 14190-1993 method of polymkeric substance acid number is measured.
The mechanical property of material adopts BG/T1040.2-2006 on universal testing machine, GB/1843-2008, and GB/T2918-1998, GB/T17037.1-1997 standard is measured.
Claims (17)
1. aliphatic-aromatic copolyester and a PLA segmented copolymer, is characterized in that consisting of aliphatic-aromatic copolyester Q and PLA block;
Described aliphatic-aromatic copolyester and PLA segmented copolymer are PLA-Q-PLA multipolymer;
Described aliphatic-aromatic copolyester Q is comprised of following polymerization single polymerization monomer:
A) one or more are selected from the compound of aliphatic dibasic acid, cycloalkyl diprotic acid or their ester, acid anhydrides, carboxylic acid halides;
B) one or more are selected from the compound of aromatic acid or its ester, acid anhydrides, carboxylic acid halides;
C) one or more are selected from the while with two compounds that are selected from the functional group of amino, sulfydryl or hydroxyl, or the compound of their derivative with epoxy group(ing), nitrogen heterocyclic or thia ring;
D) one or more are selected from the two keys of at least one carbon-to-carbon, carbon-oxygen, carbon-nitrogen or carbon-sulphur, the unsaturated acid of carbon-to-carbon or carbon-nitrogen triple bond or its ester, acid anhydrides, carboxylic acid halides; Or with the unsaturated alcohol of at least one carbon-to-carbon double bond or carbon-to-carbon triple bond or the compound of its epoxide;
Described aliphatic-aromatic copolyester is to be mixed by esterification, polycondensation by above-mentioned polymerization single polymerization monomer, then under the effect of initiator, makes polymerization single polymerization monomer D) on two keys and triple bond generation polymerization, grafting and/or linked reaction and make;
This aliphatic-aromatic copolyester and PLA segmented copolymer obtain by following steps:
Under the condition that catalyzer exists, with aliphatic-aromatic copolyester Q, cause rac-Lactide ring-opening polymerization and obtain segmented copolymer PLA-Q-PLA, described catalyzer is organo-metallic catalyst, and the consumption of described catalyzer is 0.01～5% of PLA-Q-PLA multipolymer total amount.
2. a kind of aliphatic-aromatic copolyester as claimed in claim 1 and PLA segmented copolymer, the number-average molecular weight that it is characterized in that described PLA-Q-PLA multipolymer is 10000～300000, and molecular weight distribution is 1.0～4.0, wherein the number-average molecular weight of aliphatic-aromatic copolyester Q is 2000～250000.
3. a kind of aliphatic-aromatic copolyester as claimed in claim 1 and PLA segmented copolymer, is characterized in that described organo-metallic catalyst is at least one or its mixture in organic bases earth metal compound, organo-transition metal compound, rare earth organic compounds, aluminium, germanium, tin, antimony organic compound.
4. a kind of aliphatic-aromatic copolyester as claimed in claim 1 and PLA segmented copolymer, is characterized in that described organo-metallic catalyst is one or more mixtures in stannous octoate, stannous octoate, zinc ethyl, aluminium isopropoxide, tetraisopropoxy titanium or ferric acetyl acetonade.
5. a kind of aliphatic-aromatic copolyester as claimed in claim 1 and PLA segmented copolymer, is characterized in that described aliphatic-aromatic copolyester Q and the consumption of rac-Lactide are 1～99:99～1.
6. a kind of aliphatic-aromatic copolyester as claimed in claim 1 and PLA segmented copolymer, is characterized in that described aliphatic-aromatic copolyester Q and the consumption of rac-Lactide are 20～80:80～20.
7. a kind of aliphatic-aromatic copolyester as claimed in claim 1 and PLA segmented copolymer, is characterized in that described aliphatic-aromatic copolyester and PLA block copolymer reacting temperature are at 80 ℃～300 ℃.
8. a kind of aliphatic-aromatic copolyester as claimed in claim 1 and PLA segmented copolymer, is characterized in that described aliphatic-aromatic copolyester and PLA block copolymer reacting temperature are at 110 ℃～220 ℃.
9. a kind of aliphatic-aromatic copolyester as claimed in claim 1 and PLA segmented copolymer, is characterized in that described aliphatic-aromatic copolyester and PLA block copolymer reacting time are 0.5～48 hour.
10. a kind of aliphatic-aromatic copolyester as claimed in claim 1 and PLA segmented copolymer, is characterized in that described aliphatic-aromatic copolyester and PLA block copolymer reacting time are 6～24 hours.
The PLA material of 11. 1 kinds of modifications, is characterized in that comprising PLA and PLA-Q-PLA multipolymer as claimed in claim 1.
The PLA material of 12. a kind of modifications as claimed in claim 11, is characterized in that the weight of described PLA-Q-PLA multipolymer accounts for 1～99.9% of blend total amount.
The PLA material of 13. a kind of modifications as claimed in claim 12, is characterized in that the weight of described PLA-Q-PLA multipolymer accounts for 10%～50% of blend total amount.
The aliphatic-aromatic copolyester Q material of 14. 1 kinds of modifications, is characterized in that comprising aliphatic-aromatic copolyester Q as claimed in claim 1 and PLA-Q-PLA multipolymer as claimed in claim 1.
The aliphatic-aromatic copolyester Q material of 15. a kind of modifications as claimed in claim 14, is characterized in that the weight of described PLA-Q-PLA multipolymer accounts for 1～99.9% of blend total amount.
The aliphatic-aromatic copolyester Q material of 16. a kind of modifications as claimed in claim 14, is characterized in that the weight of described PLA-Q-PLA multipolymer accounts for 10%～50% of blend total amount.
17. a kind of aliphatic-aromatic copolyester as claimed in claim 1 and PLA segmented copolymers, its application in biodegradable material.
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| CN103788599B (en) * | 2012-10-29 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of poly(lactic acid)-polyester composite and preparation method thereof |
| CN105440605B (en) * | 2014-08-29 | 2018-01-12 | 中国科学院长春应用化学研究所 | A kind of polylactic resin |
| CN105368019B (en) * | 2014-08-29 | 2017-04-19 | 中国科学院长春应用化学研究所 | Polylactic acid stereo complex |
| CN104387736B (en) * | 2014-11-18 | 2016-07-06 | 中国科学院长春应用化学研究所 | A kind of polylactic acid stereo complex |
| CN104327471B (en) * | 2014-11-18 | 2017-02-22 | 中国科学院长春应用化学研究所 | Polylactic acid three-dimensional complex |
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| CN102060986A (en) * | 2010-11-30 | 2011-05-18 | 中国科学院宁波材料技术与工程研究所 | Aromatic-aliphatic block copolyester and preparation method thereof |
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