CN113461916A - Polylactic acid and stereocomplex elastomer thereof and preparation method - Google Patents
Polylactic acid and stereocomplex elastomer thereof and preparation method Download PDFInfo
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 148
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 143
- 229920001971 elastomer Polymers 0.000 title claims abstract description 70
- 239000000806 elastomer Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229920000728 polyester Polymers 0.000 claims abstract description 124
- 229920001400 block copolymer Polymers 0.000 claims abstract description 85
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 150000002596 lactones Chemical class 0.000 claims abstract description 11
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 8
- 229920005862 polyol Polymers 0.000 claims abstract description 7
- 150000003077 polyols Chemical class 0.000 claims abstract description 7
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 46
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 25
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 19
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 15
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 10
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 8
- 229940022769 d- lactic acid Drugs 0.000 claims description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001746 injection moulding Methods 0.000 claims description 6
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 5
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 5
- 239000000600 sorbitol Substances 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- 229920001434 poly(D-lactide) Polymers 0.000 claims description 3
- PXRBWNLUQYZAAX-UHFFFAOYSA-N 6-Butyltetrahydro-2H-pyran-2-one Chemical compound CCCCC1CCCC(=O)O1 PXRBWNLUQYZAAX-UHFFFAOYSA-N 0.000 claims description 2
- FYTRVXSHONWYNE-UHFFFAOYSA-N delta-octanolide Chemical compound CCCC1CCCC(=O)O1 FYTRVXSHONWYNE-UHFFFAOYSA-N 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 238000012958 reprocessing Methods 0.000 abstract description 6
- 229920001169 thermoplastic Polymers 0.000 abstract description 6
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 238000001035 drying Methods 0.000 description 22
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- 239000000243 solution Substances 0.000 description 19
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- 230000001376 precipitating effect Effects 0.000 description 12
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- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 238000010345 tape casting Methods 0.000 description 7
- 239000013557 residual solvent Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 4
- 239000012620 biological material Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 2
- 238000007723 die pressing method Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- -1 cyclic lactones Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000118 poly(D-lactic acid) Polymers 0.000 description 1
- 229940065514 poly(lactide) Drugs 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
Abstract
The invention provides a polylactic acid and a stereocomplex elastomer thereof and a preparation method, comprising the following steps: polyol and lactone monomers react to obtain a polyhydroxy functional polyester macroinitiator; the polyhydroxy functionalized polyester macroinitiator and levorotatory lactide or dextrorotatory lactide are melted and polymerized under the action of a catalyst to obtain a multi-arm branched polyester/polylactic acid segmented copolymer; adding the multi-arm branched polyester/polylactic acid block copolymer and 2 (6-isocyanate-ureide) -6-methyl 4[1H ] -pyrimidone into toluene, and reacting under the action of a catalyst to obtain an end group functionalized multi-arm branched polyester/polylactic acid block copolymer; preparing the end group functionalized multi-arm branched polyester/polylactic acid segmented copolymer into a film to obtain the polylactic acid elastomer or the polylactic acid stereocomplex elastomer with the network structure. Solves the problems that the prior elastomer material generally has poor performances of high strength, high heat resistance, degradability, thermoplastic recovery and reprocessing.
Description
Technical Field
The invention relates to the technical field of biological materials, in particular to polylactic acid, a stereocomplex elastomer thereof and a preparation method thereof.
Background
The elastomer material is a high polymer material with high elastic performance, and has irreplaceable effects in various fields such as biological materials, intelligent materials, industrial manufacturing and the like. In order to improve the mechanical properties and heat resistance of elastomer materials, various crosslinked elastomer materials have been developed, and among them, chemically crosslinked elastomer materials have been mainly used. Despite the great improvement in mechanical properties and heat resistance of these elastomeric materials, the field of application of elastomeric materials is also expanded. However, high chemical crosslink density elastomeric materials can neither be degraded nor thermoplastically reprocessed. The other type is mainly a physical crosslinking and reversible chemical crosslinking thermoplastic elastomer material, and the elastomer can show rubber elasticity at normal temperature and can be plasticized and molded at high temperature. Overall, compared to chemically crosslinked elastomer materials, thermoplastic elastomers have significant performance advantages in terms of performance, machine-shaping processes, and recycling. However, these elastomeric materials have poor heat resistance, which limits their use in certain applications.
However, the existing elastomer material can not meet the requirements of high strength, high heat resistance, degradability and recycled thermoplastic reprocessing performance, and the wide application of the elastomer material in more fields is seriously hindered.
Disclosure of Invention
In order to overcome the defects that an elastomer material cannot simultaneously meet the requirements of high strength, high heat resistance, degradability and thermoplastic recycling reprocessing performance, the invention provides polylactic acid, a stereocomplex elastomer thereof and a preparation method.
The technical scheme adopted by the invention is that,
a preparation method of polylactic acid and a stereocomplex elastomer thereof comprises the following steps:
polyol and lactone monomers react under the action of a catalyst to obtain a polyhydroxy functional polyester macroinitiator;
the polyhydroxy functionalized polyester macroinitiator and levorotatory lactide or dextrorotatory lactide are melted and polymerized under the action of a catalyst to obtain a multi-arm branched polyester/levorotatory polylactic acid block copolymer or a multi-arm branched polyester/dextrorotatory polylactic acid block copolymer;
adding the multi-arm branched polyester/L-polylactic acid block copolymer and/or the multi-arm branched polyester/D-polylactic acid block copolymer and 2 (6-isocyanate-ureido) -6-methyl 4[1H ] -pyrimidone into toluene, and reacting under the action of a catalyst to obtain an end group functionalized multi-arm branched polyester/polylactic acid block copolymer;
wherein the end group functionalized multi-arm branched polyester/polylactic acid block copolymer comprises an end group functionalized multi-arm branched polyester/poly-L-lactic acid block copolymer, an end group functionalized multi-arm branched polyester/poly-D-lactic acid block copolymer or a mixture of the end group functionalized multi-arm branched polyester/poly-L-lactic acid block copolymer and the end group functionalized multi-arm branched polyester/poly-D-lactic acid block copolymer;
preparing the end group functionalized multi-arm branched polyester/polylactic acid segmented copolymer into a film to obtain the polylactic acid elastomer or the polylactic acid stereocomplex elastomer with the network structure.
As a further improvement of the invention, the catalyst is stannous octoate or dibutyltin dilaurate, and the using amount of the catalyst is 0.05-1.0% of the total lactone monomer or lactide, or 0.5-5.0% of the multi-arm branched polyester/polylactic acid block copolymer.
As a further improvement of the invention, the polyhydric alcohol is one or more of 1,1, 1-trimethylolpropane, pentaerythritol and sorbitol.
As a further improvement of the invention, the lactone monomers are any two of delta-valerolactone, epsilon-caprolactone, delta-nonalactone, delta-octalactone and gamma-butyrolactone, and the mass ratio of the two lactone monomers is (10-1): (1-10), the ratio of the total amount of the two substances to the amount of the polyol substance is (30-200): 1.
As a further improvement of the invention, the mole ratio of the levorotatory lactide or dextrorotatory lactide to the polyhydroxy functional polyester macroinitiator repeating unit is (2-1): (1-10).
As a further improvement of the invention, the mass ratio of the multi-arm branched polyester/L-polylactic acid block copolymer and/or the multi-arm branched polyester/D-polylactic acid block copolymer to 2 (6-isocyanate-ureide) -6-methyl 4[1H ] -pyrimidinone is (2-1): (1-4).
As a further improvement of the invention, the mass ratio of the multi-arm branched polyester/poly (L-lactic acid) block copolymer to the multi-arm branched polyester/poly (D-lactic acid) block copolymer is (0-10): (10-0).
As a further improvement of the invention, the method for preparing the film is a die pressing method, a tape casting film forming method or injection molding of an injection molding machine.
Polylactic acid and a stereocomplex elastomer thereof, which are prepared by the method.
Compared with the prior art, the invention has the following advantages:
the invention provides a preparation method of polylactic acid and a stereocomplex elastomer thereof, which takes several common polyols and cyclic lactones as raw materials, synthesizes multi-arm branched polyester/polylactic acid block copolymers through continuous ring-opening polymerization, then carries out end functionalization on the multi-arm branched polyester/polylactic acid block copolymers to synthesize end group functionalized multi-arm branched polyester/polylactic acid block copolymers, and prepares the polylactic acid elastomer or the stereocomplex elastomer of the polylactic acid with a dynamic network structure through a tape casting method or a mould pressing method. The polylactic acid elastomer and the polylactic acid stereocomplex elastomer prepared by the method have the performance advantages of high strength, high heat resistance, degradability, recovery of thermoplastic and reprocessing and the like, solve the problem that the existing elastomer material generally has the performance defects of high strength, high heat resistance, degradability, recovery of thermoplastic and reprocessing, are easy to regulate and control through controlling the structure and composition, and have high application value and popularization prospect.
The elastomer obtained by the invention has excellent mechanical property, heat resistance and hydrolysis resistance, the tensile strength of the elastomer is 6.0-31.0 MPa, the elongation at break is 500-2100%, and the performance is superior to that of common biological elastomer materials.
Drawings
FIG. 1 is a dynamic thermodynamic property test curve of polylactic acid stereocomplex elastomer obtained in example 1;
FIG. 2 is a tensile stress-strain curve of the polylactic acid elastomer obtained in example 2;
FIG. 3 is a differential scanning calorimeter test curve of the polylactic acid elastomer obtained in example 3;
FIG. 4 is an X-ray diffractometer test curve of the polylactic acid stereocomplex elastomer obtained in example 4;
FIG. 5 is an optical photograph of the polylactic acid elastomer obtained in example 5.
Detailed Description
The polylactic acid is a polyester synthesized by taking plant resources as raw materials, has good biodegradability and biocompatibility, and is an important biological material. However, the brittleness of the polylactic acid material itself limits its application. Therefore, the development of polylactic acid-based elastomer materials is an important approach for expanding the application of polylactic acid-based materials. Polylactic acid is classified into levorotatory polylactic acid, dextrorotatory polylactic acid, meso-polylactic acid, and the like because of the presence of a chiral carbon atom in a monomer molecule. The existing literature data (the formation of polylactic acid blend stereocomplex and the research progress of the performance of the polylactic acid blend stereocomplex, high molecular report, 2015, (08), 8-16; the latest research progress and application prospect of polylactic acid stereocomplex, high molecular report, 2011, (01), 33-39) have reported that the polylactic acid stereocomplex is formed between levorotatory polylactic acid and dextrorotatory polylactic acid through hydrogen bond interaction. Compared with the levorotatory polylactic acid and the dextrorotatory polylactic acid, the thermal performance of the polylactic acid stereocomplex is obviously improved. Therefore, the polylactic acid-based elastomer and the polylactic acid-based stereocomplex elastomer are developed to solve the defects that the existing elastomer material cannot be degraded or recycled for thermoplastic reprocessing, and the heat resistance is poor.
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
The invention provides a preparation method of a polylactic acid elastomer with a network structure and a polylactic acid stereocomplex elastomer, which comprises the following steps: firstly, taking polyhydric alcohol and lactone monomers as raw materials to synthesize a polyhydroxy functionalized polyester macroinitiator; then, mixing the polyhydroxy functionalized polyester macroinitiator with levorotatory lactide (or dextrorotatory lactide), and carrying out melt polymerization to prepare a multi-arm branched polyester/levorotatory polylactic acid block copolymer (or dextrorotatory polylactic acid block copolymer); reacting multi-arm branched polyester/L-polylactic acid block copolymer, multi-arm branched polyester/D-polylactic acid block copolymer and 2 (6-isocyanate-hexamethylene carbamido) -6-methyl 4[1H ] -pyrimidone to prepare end group functionalized multi-arm branched polyester/polylactic acid block copolymer; and (3) forming a film on the end group functionalized multi-arm branched polyester/polylactic acid segmented copolymer to obtain the polylactic acid elastomer or the polylactic acid stereocomplex elastomer with the dynamic network structure.
Specifically, the method comprises the following steps.
(1) Taking polyhydric alcohol and lactone monomers as raw materials, heating to 110-140 ℃ in an inert gas atmosphere, adding stannous octoate or dibutyltin dilaurate, carrying out reflux reaction for 12-24 h, cooling, dissolving in dichloromethane, precipitating with methanol, and drying to obtain a polyhydroxy functionalized polyester macroinitiator;
wherein, the polyalcohol in the step (1) is one, two or all of 1,1, 1-trimethylolpropane, pentaerythritol and sorbitol. The polyester monomer is one or more of caprolactone, valerolactone, sorbitol and the like, and the four monomers can be in any proportion.
(2) Mixing a polyhydroxy functional polyester macroinitiator and levorotatory lactide (or dextrorotatory lactide), removing water and residual solvent, heating to 120-150 ℃ in an inert gas atmosphere, adding stannous octoate or dibutyltin dilaurate, refluxing, stirring, reacting for 24-48 h, cooling, dissolving in dichloromethane, precipitating with methanol, and drying to obtain a multi-arm branched polyester/levorotatory polylactic acid block copolymer (or multi-arm branched polyester/dextrorotatory polylactic acid block copolymer);
wherein, the mol ratio of the lactide to the polyhydroxy functional polyester macroinitiator repeating unit in the step (2) is (2-1) to (1-10).
(3) Adding a multi-arm branched polyester/levorotatory polylactic acid block copolymer, a multi-arm branched polyester/dextrorotatory polylactic acid block copolymer and 2 (6-isocyanate ureido) -6-methyl 4[1H ] -pyrimidone into toluene, refluxing and stirring until the mixture is dissolved, heating to 100-130 ℃, adding stannous octoate or dibutyltin dilaurate, refluxing and stirring for reaction for 16-48H, separating and purifying the unreacted redundant 2 (6-isocyanate ureido) -6-methyl 4[1H ] -pyrimidone and a solvent after the reaction is finished, and drying to obtain the end group functionalized multi-arm branched polyester/polylactic acid block copolymer;
wherein, the mass ratio of the multi-arm branched polyester/L-polylactic acid block copolymer, the multi-arm branched polyester/D-polylactic acid block copolymer and the 2 (6-isocyanate-carbamido) -6-methyl 4[1H ] -pyrimidinone in the step (3) is (2-1): 1-4. The mass ratio of the multi-arm branched polyester/levorotatory polylactic acid block copolymer to the multi-arm branched polyester/dextrorotatory polylactic acid block copolymer in the step (3) is (0-10): (10-0). If 0 part of one raw material is taken to indicate that no corresponding raw material is added, and 10 parts of the other raw material are taken.
(4) The end group functionalized multi-arm branched polyester/polylactic acid segmented copolymer is prepared into a film by adopting a mould pressing method, a tape casting method or an injection molding machine for injection molding, namely the polylactic acid elastomer or the polylactic acid stereo composite elastomer with a dynamic network structure.
The present invention will be described in detail below with reference to specific embodiments and the accompanying drawings.
Example 1
(1) Adding pentaerythritol, delta-valerolactone and epsilon-caprolactone into a three-neck flask, heating to 120 ℃ in nitrogen atmosphere, adding stannous octoate to react for 24 hours, cooling, dissolving in dichloromethane, precipitating with methanol, and drying to obtain a polyhydroxy functionalized polyester macroinitiator, wherein the mass ratio of the total mass of the delta-valerolactone and the epsilon-caprolactone to the mass of an initiator is 100:1, and the mass ratio of the delta-valerolactone and the epsilon-caprolactone is 2: 8; the using amount of the stannous octoate is 0.1 percent of the total amount of delta-valerolactone and epsilon-caprolactone;
(2) adding a polyhydroxy functional polyester macroinitiator and levorotatory lactide (or dextrorotatory lactide) into a three-mouth flask, removing water and residual solvent, heating to 120 ℃ in nitrogen atmosphere, adding stannous octoate to react for 48 hours, cooling, dissolving in dichloromethane, precipitating with methanol, and drying to obtain a multi-arm branched polyester/levorotatory polylactic acid block copolymer (or a multi-arm branched polyester/dextrorotatory polylactic acid block copolymer), wherein the molar ratio of repeating units of the lactide and the polyhydroxy functional polyester macroinitiator is 1: 2; the using amount of the stannous octoate is 0.1 percent of that of the lactide substance;
(3) adding a multi-arm branched polyester/poly (L-lactide) block copolymer, a multi-arm branched polyester/poly (D-lactide) block copolymer, 2 (6-isocyanate-uretonio) -6-methyl 4[1H ] -pyrimidone and toluene into a three-neck flask, heating to 110 ℃, refluxing and stirring to dissolve for 1H, adding stannous octoate, continuing to reflux and stir for reaction for 24H, separating and purifying after the reaction is finished to remove unreacted 2 (6-isocyanate-uretonio) -6-methyl 4[1H ] -pyrimidone and solvent, and drying to obtain a mixture of the end group functionalized multi-arm branched polyester/poly (L-lactide) block copolymer and the end group functionalized multi-arm branched polyester/poly (D-lactide) block copolymer, wherein the 2 (6-isocyanate-uretonio) -6-methyl 4[1H ] -pyrimidone and the multi-arm branched polyester/poly (lactide) block copolymer The mass ratio of the poly (lactic acid) to the poly (lactic acid) is 1:1, and the mass ratio of the multi-arm branched polyester/poly (lactic acid) to the multi-arm branched polyester/poly (lactic acid) is 5: 5; the using amount of the stannous octoate is 3.0 percent of the mass of the multi-arm branched polyester/polylactic acid block copolymer;
(4) melting the end group functionalized multi-arm branched polyester/polylactic acid segmented copolymer at 180 ℃ by adopting a die pressing method, then cooling to room temperature under the pressure of 8MPa to obtain the stereo composite polylactic acid elastomer.
The obtained polylactic acid stereocomplex elastomer has the tensile strength of 16.8MPa and the elongation at break of 720 percent. FIG. 1 is a dynamic thermodynamic property test curve of polylactic acid stereocomplex elastomer obtained in example 1. The heat resistance of the prepared polylactic acid stereocomplex elastomer is obviously improved, and the heat resistance temperature can reach about 140 ℃.
Example 2
(1) Adding pentaerythritol, delta-valerolactone and epsilon-caprolactone into a three-neck flask, heating to 120 ℃ in a nitrogen atmosphere, adding stannous octoate, carrying out reflux reaction for 48 hours, cooling, dissolving in dichloromethane, precipitating with methanol, and drying to obtain a polyhydroxy functionalized polyester macroinitiator, wherein the mass ratio of the total mass of the delta-valerolactone and the epsilon-caprolactone to the mass of the pentaerythritol is 100:1, and the mass ratio of the delta-valerolactone and the epsilon-caprolactone is 3: 7; the using amount of the stannous octoate is 0.1 percent of the total amount of delta-valerolactone and epsilon-caprolactone;
(2) adding a polyhydroxy functional polyester macroinitiator and dextrorotatory polylactic acid into a three-mouth flask, removing water and residual solvent, heating to 130 ℃ in a nitrogen atmosphere, adding stannous octoate for reacting for 48 hours, cooling, dissolving in dichloromethane, precipitating with methanol, and drying to obtain a multi-arm branched polyester/dextrorotatory polylactic acid block copolymer, wherein the molar ratio of repeating units of lactide and the polyhydroxy functional polyester macroinitiator is 1: 2; the using amount of the stannous octoate is 0.1 percent of that of the lactide substance;
(3) adding multi-arm branched polyester/right-handed polylactic acid block copolymer, 2 (6-isocyanate-ureido) -6-methyl 4[1H ] -pyrimidone and toluene into a three-mouth flask, heating to 110 ℃, refluxing and stirring until the mixture is dissolved for 2H, adding dibutyltin dilaurate, continuously refluxing and stirring for reaction for 48H, after the reaction is finished, separating, purifying and removing the excessive unreacted 2 (6-isocyanate-urethano) -6-methyl 4[1H ] -pyrimidone and solvent, drying to obtain the end group functionalized multi-arm branched polyester/levorotatory polylactic acid block copolymer, wherein the mass ratio of the 2 (6-isocyanate-ureide) -6-methyl 4[1H ] -pyrimidone to the multi-arm branched polyester/poly-D-lactic acid block copolymer is 1: 1; the using amount of the dibutyltin dilaurate is 2.0 percent of the mass of the multi-arm branched polyester/polylactic acid block copolymer;
(4) adopting a tape casting film forming method, dissolving the end group functionalized multi-arm branched polyester/dextrorotatory polylactic acid segmented copolymer chloroform with the concentration of about 10mg/mL, placing the solution in a mould, standing the solution at room temperature until the solution is completely volatilized, and drying the solution at 30 ℃ for 48 hours to obtain the polylactic acid elastomer.
The obtained polylactic acid elastomer had a tensile strength of 7.20MPa and an elongation at break of 760%. FIG. 2 is a tensile stress-strain curve of the polylactic acid elastomer obtained in this example. The prepared polylactic acid elastomer can generate obvious deformation under smaller stress.
Example 3
(1) Adding sorbitol, delta-valerolactone and epsilon-caprolactone into a three-neck flask, heating to 130 ℃ in a nitrogen atmosphere, adding dibutyltin dilaurate, carrying out reflux reaction for 36 hours, cooling, dissolving in dichloromethane, precipitating with methanol, and drying to obtain a polyhydroxy functionalized polyester macroinitiator, wherein the mass ratio of the total mass of the delta-valerolactone and the epsilon-caprolactone to the mass of pentaerythritol is 100:1, and the mass ratio of the delta-valerolactone to the epsilon-caprolactone is 2: 8; the dosage of the dibutyltin dilaurate is 0.1 percent of the total amount of delta-valerolactone and epsilon-caprolactone;
(2) adding a polyhydroxy functional polyester macroinitiator and levorotatory lactide into a three-neck flask, removing water and residual solvent, heating to 140 ℃ in nitrogen atmosphere, adding stannous octoate for reacting for 36 hours, cooling, dissolving in dichloromethane, precipitating with methanol, and drying to obtain a multi-arm branched polyester/levorotatory polylactic acid block copolymer, wherein the molar ratio of repeating units of the lactide to the polyhydroxy functional polyester macroinitiator is 1: 4; the using amount of the stannous octoate is 0.1 percent of that of the lactide substance;
(3) adding multi-arm branched polyester/levorotatory polylactic acid block copolymer, 2 (6-isocyanate-ureido) -6-methyl 4[1H ] -pyrimidone and toluene into a three-mouth flask, heating to 110 ℃, refluxing and stirring until the mixture is dissolved for 1H, adding dibutyltin dilaurate, continuously refluxing and stirring for reaction for 48H, after the reaction is finished, separating, purifying and removing the excessive unreacted 2 (6-isocyanate-urethano) -6-methyl 4[1H ] -pyrimidone and solvent, drying to obtain the end group functionalized multi-arm branched polyester/levorotatory polylactic acid block copolymer, wherein the mass ratio of the 2 (6-isocyanate-ureide) -6-methyl 4[1H ] -pyrimidone to the multi-arm branched polyester/L-polylactic acid block copolymer is 1: 1; the using amount of the dibutyltin dilaurate is 3.0 percent of the mass of the multi-arm branched polyester/levorotatory polylactic acid block copolymer;
(4) adopting a tape casting film forming method, dissolving the end group functionalized multi-arm branched polyester/levorotatory polylactic acid block copolymer in chloroform to obtain a solution with the concentration of about 10mg/mL, placing the solution in a mold, standing the solution at room temperature until the solution is completely volatilized, and drying the solution at 30 ℃ for 48 hours to obtain the polylactic acid elastomer.
The obtained polylactic acid elastomer has a tensile strength of 12.6MPa and an elongation at break of 960%. FIG. 3 is a differential scanning calorimeter test curve of the polylactic acid elastomer obtained in this example. The glass transition size of the prepared polylactic acid elastomer is about-40 ℃, and weak cold crystallization peaks and melting peaks of the polylactic acid appear at 100 ℃ and 130 ℃ on a secondary heating curve respectively.
Example 4
(1) Adding 1,1, 1-trimethylolpropane, delta-valerolactone and epsilon-caprolactone into a three-neck flask, heating to 130 ℃ in nitrogen atmosphere, adding stannous octoate for reacting for 20 hours, cooling, dissolving in dichloromethane, precipitating with methanol, and drying to obtain a polyhydroxy functional polyester macroinitiator, wherein the mass ratio of the total mass of the delta-valerolactone and the epsilon-caprolactone to the initiator is 100:1, and the mass ratio of the delta-valerolactone and the epsilon-caprolactone is 2: 8; the using amount of the stannous octoate is 0.1 percent of the total amount of delta-valerolactone and epsilon-caprolactone;
(2) adding a polyhydroxy functional polyester macroinitiator and levorotatory lactide (or dextrorotatory lactide) into a three-mouth flask, removing water and residual solvent, heating to 130 ℃ in nitrogen atmosphere, adding stannous octoate to react for 24 hours, cooling, dissolving in dichloromethane, precipitating with methanol, and drying to obtain a multi-arm branched polyester/levorotatory polylactic acid block copolymer (or multi-arm branched polyester/dextrorotatory polylactic acid block copolymer), wherein the molar ratio of repeating units of the lactide and the polyhydroxy functional polyester macroinitiator is 1: 2; the using amount of the stannous octoate is 0.1 percent of that of the lactide substance;
(3) adding a multi-arm branched polyester/poly-L-lactic acid block copolymer, a multi-arm branched polyester/poly-D-lactic acid block copolymer, 2 (6-isocyanate-uretonio) -6-methyl 4[1H ] -pyrimidone and toluene into a three-mouth flask, heating to 110 ℃, refluxing and stirring until the mixture is dissolved for 2H, adding dibutyltin dilaurate, continuing to reflux and stir for reaction for 20H, separating and purifying to remove the residual unreacted 2 (6-isocyanate-uretonio) -6-methyl 4[1H ] -pyrimidone and solvent after the reaction is finished, and drying to obtain a mixture of the end group functionalized multi-arm branched polyester/poly-L-lactic acid block copolymer and the end group functionalized multi-arm branched polyester/poly-D-lactic acid block copolymer, wherein the 2 (6-isocyanate-uretonio) -6-methyl 4[1H ] -pyrimidone and the multi-arm branched polyester/poly-D-lactic acid block copolymer The mass ratio of the lactic acid block copolymer is 1:1, and the mass ratio of the multi-arm branched polyester/levorotatory polylactic acid block copolymer to the multi-arm branched polyester/dextrorotatory polylactic acid block copolymer is 7: 3; the using amount of the dibutyltin dilaurate is 3.0 percent of the mass of the multi-arm branched polyester/polylactic acid block copolymer;
(4) adopting a tape casting film forming method, dissolving the end group functionalized multi-arm branched polyester/polylactic acid segmented copolymer chloroform with the concentration of about 10mg/mL, placing the solution in a mould, standing the solution at room temperature until the solution is completely volatilized, and drying the solution at 30 ℃ for 48 hours to obtain the stereo composite polylactic acid elastomer.
The obtained polylactic acid stereocomplex elastomer has the tensile strength of 25.6MPa and the elongation at break of 1570 percent. FIG. 4 is an X-ray diffractometer test curve of the polylactic acid stereocomplex elastomer obtained in example 4. The prepared polylactic acid stereocomplex elastomer has diffraction peaks of (110), (300)/(030) planes of beta crystals formed by stereocomplex polylactic acid at 2 theta of 12.0 DEG and 20.9 deg.
Example 5
(1) Adding 1,1, 1-trimethylolpropane, delta-valerolactone and epsilon-caprolactone into a three-neck flask, heating to 120 ℃ in a nitrogen atmosphere, adding stannous octoate, carrying out reflux reaction for 24 hours, cooling, dissolving in dichloromethane, precipitating with methanol, and drying to obtain a polyhydroxy functionalized polyester macroinitiator, wherein the mass ratio of the total mass of the delta-valerolactone and the epsilon-caprolactone to the mass of the 1,1, 1-trimethylolpropane is 100:1, and the mass ratio of the delta-valerolactone and the epsilon-caprolactone is 2: 8; the using amount of the stannous octoate is 0.1 percent of the total amount of delta-valerolactone and epsilon-caprolactone;
(2) adding a polyhydroxy functional polyester macroinitiator and levorotatory lactide into a three-neck flask, removing water and residual solvent, heating to 130 ℃ in a nitrogen atmosphere, adding stannous octoate, refluxing, stirring and reacting for 24 hours, cooling, dissolving in dichloromethane, precipitating with methanol, and drying to obtain a multi-arm branched polyester/levorotatory polylactic acid block copolymer, wherein the molar ratio of repeating units of the lactide to the polyhydroxy functional polyester macroinitiator is 1: 2; the using amount of the stannous octoate is 0.1 percent of that of the lactide substance;
(3) adding multi-arm branched polyester/levorotatory polylactic acid block copolymer, 2 (6-isocyanate-ureido) -6-methyl 4[1H ] -pyrimidone and toluene into a three-mouth flask, heating to 110 ℃, refluxing and stirring until the mixture is dissolved for 1H, adding dibutyltin dilaurate, continuously refluxing and stirring for reaction for 24H, after the reaction is finished, separating, purifying and removing the excessive unreacted 2 (6-isocyanate-urethano) -6-methyl 4[1H ] -pyrimidone and solvent, drying to obtain the end group functionalized multi-arm branched polyester/levorotatory polylactic acid block copolymer, wherein the mass ratio of the 2 (6-isocyanate-ureide) -6-methyl 4[1H ] -pyrimidone to the multi-arm branched polyester/L-polylactic acid block copolymer is 0.6: 1; the using amount of the dibutyltin dilaurate is 3.0 percent of the mass of the multi-arm branched polyester/levorotatory polylactic acid block copolymer;
(4) adopting a tape casting film forming method, dissolving the end group functionalized multi-arm branched polyester/levorotatory polylactic acid block copolymer in chloroform to obtain a solution with the concentration of about 20mg/mL, placing the solution in a mold, standing the solution at room temperature until the solution is completely volatilized, and drying the solution at 30 ℃ for 48 hours to obtain the polylactic acid elastomer.
The obtained polylactic acid elastomer has a tensile strength of 9.60MPa and an elongation at break of 610%. FIG. 5 is an optical photograph of the polylactic acid elastomer obtained in the present example. The prepared polylactic acid elastomer has good light transmittance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (9)
1. A preparation method of polylactic acid and a stereocomplex elastomer thereof is characterized by comprising the following steps:
polyol and lactone monomers react under the action of a catalyst to obtain a polyhydroxy functional polyester macroinitiator;
the polyhydroxy functionalized polyester macroinitiator and levorotatory lactide or dextrorotatory lactide are melted and polymerized under the action of a catalyst to obtain a multi-arm branched polyester/levorotatory polylactic acid block copolymer or a multi-arm branched polyester/dextrorotatory polylactic acid block copolymer;
adding the multi-arm branched polyester/L-polylactic acid block copolymer and/or the multi-arm branched polyester/D-polylactic acid block copolymer and 2 (6-isocyanate-ureido) -6-methyl 4[1H ] -pyrimidone into toluene, and reacting under the action of a catalyst to obtain an end group functionalized multi-arm branched polyester/polylactic acid block copolymer;
wherein the end group functionalized multi-arm branched polyester/polylactic acid block copolymer comprises an end group functionalized multi-arm branched polyester/poly-L-lactic acid block copolymer, an end group functionalized multi-arm branched polyester/poly-D-lactic acid block copolymer or a mixture of the end group functionalized multi-arm branched polyester/poly-L-lactic acid block copolymer and the end group functionalized multi-arm branched polyester/poly-D-lactic acid block copolymer;
preparing the end group functionalized multi-arm branched polyester/polylactic acid segmented copolymer into a film to obtain the polylactic acid elastomer or the polylactic acid stereocomplex elastomer with the network structure.
2. The method of claim 1,
the catalyst is stannous octoate or dibutyltin dilaurate, and the dosage of the catalyst is 0.05-1.0% of the total lactone monomer or lactide, or 0.5-5.0% of the multi-arm branched polyester/polylactic acid block copolymer.
3. The method of claim 1, wherein the polyol is one or more of 1,1, 1-trimethylolpropane, pentaerythritol, and sorbitol.
4. The method according to claim 1, wherein the lactone monomer is any two of delta-valerolactone, epsilon-caprolactone, delta-nonalactone, delta-octalactone and gamma-butyrolactone, and the mass ratio of the two lactone monomers is (10-1): (1-10), the total amount of the both and the amount of the polyol material is (30-200): 1.
5. The method according to claim 1, wherein the mole ratio of the levorotatory lactide or dextrorotatory lactide to the polyhydroxy functional polyester macroinitiator repeating units is (2-1): (1-10).
6. The method according to claim 1, wherein the mass ratio of the multi-arm branched polyester/L-polylactic acid block copolymer and/or the multi-arm branched polyester/D-polylactic acid block copolymer to the 2 (6-isocyanateureyl) -6-methyl 4[1H ] -pyrimidinone is (2-1): (1-4).
7. The method according to claim 1, wherein the mass ratio of the multi-arm branched polyester/poly (L-lactide) block copolymer to the multi-arm branched polyester/poly (D-lactide) block copolymer is (0-10): (10-0).
8. The method of claim 1, wherein the film is formed by molding, casting, or injection molding using an injection molding machine.
9. A polylactic acid and a stereocomplex elastomer thereof, which are produced by the method according to any one of claims 1 to 8.
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