CN113999373A - Polylactic acid-polyethylene glycol succinate copolymer and preparation method thereof - Google Patents
Polylactic acid-polyethylene glycol succinate copolymer and preparation method thereof Download PDFInfo
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 67
- 239000002202 Polyethylene glycol Substances 0.000 title claims abstract description 44
- 229920001223 polyethylene glycol Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- DJIHQRBJGCGSIR-UHFFFAOYSA-N 2-methylidene-1,3-dioxepane-4,7-dione Chemical compound C1(CCC(=O)OC(=C)O1)=O DJIHQRBJGCGSIR-UHFFFAOYSA-N 0.000 claims abstract description 18
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims abstract description 18
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 45
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- 239000001384 succinic acid Substances 0.000 claims description 15
- 238000005886 esterification reaction Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- HFVMEOPYDLEHBR-UHFFFAOYSA-N (2-fluorophenyl)-phenylmethanol Chemical compound C=1C=CC=C(F)C=1C(O)C1=CC=CC=C1 HFVMEOPYDLEHBR-UHFFFAOYSA-N 0.000 claims description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 3
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- -1 polybutylene succinate Polymers 0.000 description 10
- 239000004626 polylactic acid Substances 0.000 description 10
- 229920000747 poly(lactic acid) Polymers 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 229920002961 polybutylene succinate Polymers 0.000 description 7
- 239000004631 polybutylene succinate Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 6
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- LOWXIIGCOBSYKX-UHFFFAOYSA-N 1,4-dioxocane-5,8-dione Chemical group O=C1CCC(=O)OCCO1 LOWXIIGCOBSYKX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001522 polyglycol ester Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
A polylactic acid-poly (ethylene succinate) copolymer and a preparation method thereof are disclosed, the preparation method of the polylactic acid-poly (ethylene succinate) copolymer is characterized in that the polylactic acid-poly (ethylene succinate) copolymer is prepared by synthesizing L-lactide and poly (ethylene succinate) prepolymer under the action of a catalyst, and the preparation method comprises the following specific steps: synthesizing prepolymer polyethylene glycol succinate; synthesizing a polylactic acid-polyethylene glycol succinate copolymer; and (4) post-treating the copolymer. The polylactic acid-polyethylene glycol succinate copolymer has good physical and mechanical properties, can be completely biodegraded, and is applied to the technical field of biodegradable copolymers.
Description
Technical Field
The invention relates to a polylactic acid-polyethylene glycol succinate copolymer and a preparation method thereof in the technical field of biodegradable copolymers.
Background
The polybutylene succinate (PBS) has good biodegradability, and simultaneously has mechanical and physical properties similar to those of general plastics due to a large number of methylene structures on a main chain, so that the polybutylene succinate can be used for preparing various completely biodegradable high polymer products, such as garbage bags, food bags, various bottles, disposable catering utensils and the like. The polyethylene succinate (PES) is a homolog of the polybutylene succinate, has good processing performance, good mechanical property and heat resistance, has the mechanical strength close to that of polyethylene (LDPE) and polypropylene (PP), is biodegradable aliphatic polyester as the polyethylene succinate (PES), has the maximum tensile strength of more than 30MPa, and has the elongation at break of 380%. Compared with the poly (butylene succinate), the poly (ethylene succinate) has the impact strength 6 times that of the poly (butylene succinate), has the biodegradation rate higher than that of the poly (butylene succinate), is lower in price, can realize complete bio-based production, and does not consume petroleum resources.
The polylactic acid is biodegradable polyester, has the advantages of high strength, good biocompatibility, degradability and the like, and has wide market prospect in the field of packaging materials. But its wide application is limited due to its brittleness, poor impact resistance, lack of flexibility, etc.
At present, in order to improve the defects of polylactic acid, polybutylene succinate and polylactic acid are blended to obtain a biodegradable blending material, wherein the polybutylene succinate can serve as a soft segment to enhance the toughness of the blending material, and the polylactic acid serves as a hard segment to improve the strength of the polybutylene succinate and improve the flowability of the polylactic acid in the processing processes of blow molding, injection molding, plastic uptake and the like. The raw material cost of the poly (ethylene succinate) is lower than that of the poly (butylene succinate), and the poly (ethylene succinate) has better comprehensive performance, so that the poly (ethylene succinate) can be partially or completely substituted for the poly (butylene succinate) to be applied to certain purposes. However, the synergistic effect between the polyglycol ester of a polydiacid and polylactic acid is not very desirable and needs further improvement. Copolymerization modification is one of the commonly used means, and a polymerization method of addition polymerization by a mixture of two or more monomers not only can maintain the performance characteristics of the copolymer itself but also can improve the performance defects of the copolymer itself by the interaction with other segments after copolymerization. Therefore, the development of a polylactic acid-polyethylene glycol succinate copolymer and a preparation method thereof are still a new problem to be solved.
Disclosure of Invention
The invention aims to provide a polylactic acid-polyethylene glycol succinate copolymer and a preparation method thereof, the polylactic acid-polyethylene glycol succinate copolymer is prepared by polycondensation of polylactic acid and polyethylene glycol succinate, and the polylactic acid-polyethylene glycol succinate copolymer and the preparation method of the polymer are provided.
The purpose of the invention is realized as follows: a polylactic acid-polyethylene glycol succinate copolymer is disclosed, wherein the structural general formula of the polylactic acid-polyethylene glycol succinate copolymer is as follows:
wherein m and n are polymerization degrees of polymerization units, and are the same or different and are natural integers; the weight average molecular weight of the copolymer is between 50100 and 78500;
the preparation method of the polylactic acid-poly (ethylene succinate) copolymer comprises the following steps of:
(1) synthesizing prepolymer polyethylene glycol succinate:
mixing ethylene glycol and succinic acid according to a molar ratio of 1.08-1.55: 1, adding the catalyst into a reaction kettle according to the mass ratio, keeping the system pressure at 0.20-0.30MPa at the temperature of 110-195 ℃ in an inert atmosphere, reacting for 4-8 hours until no small molecular fraction is evaporated, vacuumizing the obtained esterification reaction product to control the vacuum degree within 200Pa, reacting for 2-8 hours at the temperature of 170-200 ℃, and performing vacuum extrusion to obtain the poly (ethylene succinate) prepolymer;
(2) and (3) synthesis of polylactic acid-polyethylene glycol succinate copolymer:
in a reaction kettle, the mass ratio of 1-3.15: 1, adding an L-lactide and poly (ethylene succinate) prepolymer, then adding a catalyst, wherein the content of the L-lactide is 0.5-1.2 mol%, heating to 125-200 ℃ in an inert atmosphere, and reacting for 12-24 hours to obtain a poly (lactic acid-poly (ethylene succinate) copolymer;
(3) post-treatment of the copolymer:
dissolving the polylactic acid-polyethylene glycol succinate copolymer obtained in the step (2) with chloroform, precipitating with absolute ethanol, and vacuum drying at 40-50 ℃ to obtain the polylactic acid-polyethylene glycol succinate copolymer;
the catalyst is a catalyst for common esterification reaction, and more preferably any one or two of tin dioctoate, antimony trioxide, tin oxide, tetrabutyl titanate, tetrapropyl titanate and polyphosphoric acid.
The key point of the invention is the copolymer of polylactic acid-polyethylene glycol succinate and the preparation method thereof.
Compared with the prior art, the preparation method of the polylactic acid-poly (ethylene succinate) copolymer comprises the ring-opening polymerization of poly (ethylene succinate) prepolymer and L-lactide, the copolymer combines a poly (ethylene succinate) chain segment and a poly (lactic acid) chain segment, the brittleness of polylactic acid can be effectively improved, the mechanical property of poly (ethylene succinate) is kept, the poly (lactic acid-poly (ethylene succinate) copolymer has better physical and mechanical properties, can be completely biodegraded, has the advantages of wide development prospect and the like in the fields of green packaging plastic products and the like, and can be widely applied to the technical field of biodegradable copolymers.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the embodiments of the present invention are further described with reference to examples, which are only used for illustrating the present invention and do not limit the scope of the present invention.
A polylactic acid (PLA) -polyethylene glycol succinate (PES) copolymer has a structural formula as follows:
wherein m and n are polymerization degrees of polymerization units, and are the same or different and are natural integers; the weight average molecular weight of the copolymer is between 50100 and 78500.
The preparation method of the polylactic acid (PLA) -polyethylene glycol succinate (PES) copolymer comprises the following steps of:
(1) synthesizing prepolymer polyethylene glycol succinate:
mixing ethylene glycol and succinic acid according to a molar ratio of 1.08-1.55: 1, adding the catalyst into a reaction kettle according to the mass ratio, keeping the system pressure at 0.20-0.30MPa at the temperature of 110-195 ℃ in an inert atmosphere, reacting for 4-8 hours until no small molecular fraction is evaporated, vacuumizing the obtained esterification reaction product to control the vacuum degree within 200Pa, reacting for 2-8 hours at the temperature of 170-200 ℃, and performing vacuum extrusion to obtain the poly (ethylene succinate) prepolymer;
(2) and (3) synthesis of polylactic acid-polyethylene glycol succinate copolymer:
in a reaction kettle, the mass ratio of 1-3.15: 1, adding an L-lactide and poly (ethylene succinate) prepolymer, then adding a catalyst, wherein the content of the L-lactide is 0.5-1.2 mol%, heating to 125-200 ℃ in an inert atmosphere, and reacting for 12-24 hours to obtain a poly (lactic acid-poly (ethylene succinate) copolymer;
(3) post-treatment of the copolymer:
and (3) dissolving the polylactic acid-polyethylene glycol succinate copolymer obtained in the step (2) by using chloroform, precipitating by using absolute ethyl alcohol, and drying in vacuum at 40-50 ℃ to obtain the polylactic acid-polyethylene glycol succinate copolymer.
The catalyst is a catalyst for common esterification reaction, and more preferably any one or two of tin dioctoate, antimony trioxide, tin oxide, tetrabutyl titanate, tetrapropyl titanate and polyphosphoric acid.
The data in the present invention and its examples were tested according to the following standards or methods:
(1) the tensile strength and the elongation at break are tested according to GB/T1040.1 and GB/T1040.3;
(2) molecular weights were determined by Gel Permeation Chromatography (GPC).
Example one
Mixing ethylene glycol and succinic acid according to a molar ratio of 1.45: adding the mixture ratio of 1 into a reaction kettle, adding tetrabutyl titanate catalyst (the content is 0.82 percent of the total mass of succinic acid and ethylene glycol), keeping the system pressure at 0.25MPa at 175 ℃ in an inert atmosphere, reacting for 6 hours until no small molecular fraction is distilled out, then vacuumizing the obtained esterification reaction product to control the vacuum degree within 200Pa, reacting for 7 hours at 185 ℃, and performing vacuum extrusion to obtain the poly (ethylene succinate) prepolymer. The mass ratio in the reaction kettle is 2: 1, adding an L-lactide and polyethylene glycol succinate prepolymer, then adding a tin dioctoate catalyst (L-lactide with the content of 1 mol%), heating to 175 ℃ in an inert atmosphere, and reacting for 12 hours to obtain the polylactic acid-polyethylene glycol succinate copolymer. Dissolving the obtained polylactic acid-poly (ethylene succinate) copolymer with chloroform, precipitating with absolute ethanol, and vacuum drying at 45 ℃ to obtain the polylactic acid-poly (ethylene succinate) copolymer.
Example two
Mixing ethylene glycol and succinic acid according to a molar ratio of 1.45: adding the mixture ratio of 1 into a reaction kettle, adding tetrabutyl titanate catalyst (the content is 0.82 percent of the total mass of succinic acid and ethylene glycol), keeping the system pressure at 0.25MPa at 175 ℃ in an inert atmosphere, reacting for 6 hours until no small molecular fraction is distilled out, then vacuumizing the obtained esterification reaction product to control the vacuum degree within 200Pa, reacting for 7 hours at 185 ℃, and performing vacuum extrusion to obtain the poly (ethylene succinate) prepolymer. The mass ratio in the reaction kettle is 2.5: 1, adding an L-lactide and polyethylene glycol succinate prepolymer, then adding a tin dioctoate catalyst (L-lactide with the content of 1 mol%), heating to 175 ℃ in an inert atmosphere, and reacting for 12 hours to obtain the polylactic acid-polyethylene glycol succinate copolymer. Dissolving the obtained polylactic acid-poly (ethylene succinate) copolymer with chloroform, precipitating with absolute ethanol, and vacuum drying at 45 ℃ to obtain the polylactic acid-poly (ethylene succinate) copolymer.
EXAMPLE III
Mixing ethylene glycol and succinic acid according to a molar ratio of 1.45: adding the mixture ratio of 1 into a reaction kettle, adding tetrabutyl titanate catalyst (the content is 0.82 percent of the total mass of succinic acid and ethylene glycol), keeping the system pressure at 0.25MPa at 175 ℃ in an inert atmosphere, reacting for 6 hours until no small molecular fraction is distilled out, then vacuumizing the obtained esterification reaction product to control the vacuum degree within 200Pa, reacting for 7 hours at 185 ℃, and performing vacuum extrusion to obtain the poly (ethylene succinate) prepolymer. The mass ratio in the reaction kettle is 2.85: 1, adding an L-lactide and polyethylene glycol succinate prepolymer, then adding a tin dioctoate catalyst (L-lactide with the content of 1 mol%), heating to 170 ℃ in an inert atmosphere, and reacting for 12 hours to obtain the polylactic acid-polyethylene glycol succinate copolymer. Dissolving the obtained polylactic acid-poly (ethylene succinate) copolymer with chloroform, precipitating with absolute ethanol, and vacuum drying at 45 ℃ to obtain the polylactic acid-poly (ethylene succinate) copolymer.
Example four
Mixing ethylene glycol and succinic acid according to a molar ratio of 1.45: adding the mixture ratio of 1 into a reaction kettle, adding tetrabutyl titanate catalyst (the content is 0.82 percent of the total mass of succinic acid and ethylene glycol), keeping the system pressure at 0.25MPa at 175 ℃ in an inert atmosphere, reacting for 6 hours until no small molecular fraction is distilled out, then vacuumizing the obtained esterification reaction product to control the vacuum degree within 200Pa, reacting for 7 hours at 185 ℃, and performing vacuum extrusion to obtain the poly (ethylene succinate) prepolymer. The mass ratio in the reaction kettle is 1.8: 1, adding an L-lactide and polyethylene glycol succinate prepolymer, then adding a tin dioctoate catalyst (L-lactide with the content of 1 mol%), heating to 170 ℃ in an inert atmosphere, and reacting for 12 hours to obtain the polylactic acid-polyethylene glycol succinate copolymer. Dissolving the obtained polylactic acid-poly (ethylene succinate) copolymer with chloroform, precipitating with absolute ethanol, and vacuum drying at 45 ℃ to obtain the polylactic acid-poly (ethylene succinate) copolymer.
EXAMPLE five
Mixing ethylene glycol and succinic acid according to a molar ratio of 1.45: adding the mixture ratio of 1 into a reaction kettle, adding tetrabutyl titanate catalyst (the content is 0.82 percent of the total mass of succinic acid and ethylene glycol), keeping the system pressure at 0.25MPa at 175 ℃ in an inert atmosphere, reacting for 6 hours until no small molecular fraction is distilled out, then vacuumizing the obtained esterification reaction product to control the vacuum degree within 200Pa, reacting for 7 hours at 185 ℃, and performing vacuum extrusion to obtain the poly (ethylene succinate) prepolymer. The mass ratio in the reaction kettle is 1.2: 1, adding an L-lactide and polyethylene glycol succinate prepolymer, then adding a tin dioctoate catalyst (L-lactide with the content of 1 mol%), heating to 175 ℃ in an inert atmosphere, and reacting for 12 hours to obtain the polylactic acid-polyethylene glycol succinate copolymer. Dissolving the obtained polylactic acid-poly (ethylene succinate) copolymer with chloroform, precipitating with absolute ethanol, and vacuum drying at 45 ℃ to obtain the polylactic acid-poly (ethylene succinate) copolymer.
Comparative example 1
Mixing ethylene glycol and succinic acid according to a molar ratio of 1.45: adding the mixture ratio of 1 into a reaction kettle, adding tetrabutyl titanate catalyst (the content is 0.82 percent of the total mass of succinic acid and ethylene glycol), keeping the system pressure at 0.25MPa at 175 ℃ in an inert atmosphere, reacting for 6 hours until no small molecular fraction is distilled out, then vacuumizing the obtained esterification reaction product, controlling the vacuum degree within 200Pa, and reacting for 7 hours at 185 ℃. After cooling, 5wt% of isopropyl titanate is added into the reaction kettle and reacted for 1.5 hours at 145 ℃ to obtain the polyethylene glycol succinate.
TABLE 1 Property parameters of the copolymers of different molecular weights
| Numbering | Weight average molecular weight | Tensile strength MPa | Elongation at break% |
| Example one | 69500 | 36.2 | 135 |
| Example two | 71200 | 39.4 | 127 |
| Practice ofEXAMPLE III | 72400 | 33.2 | 155 |
| Example four | 75200 | 34.9 | 140 |
| EXAMPLE five | 78450 | 32.4 | 173 |
| Comparative example 1 | 94000 | 25.1 | 380 |
The data in table 1 shows that from the data for examples one through five and comparative example one it can be seen that: the polylactic acid-polyethylene glycol succinate copolymer prepared by the preparation method provided by the invention has greatly improved mechanical properties, certain tensile strength and improved toughness, and has wide development and application prospects.
The various features described in the foregoing description of the embodiments may be combined in any suitable manner without departing from the scope of the invention, and various combinations are not further described in order to avoid unnecessary repetition. In addition, any combination of the various embodiments of the present invention can be made, and the same should be considered as the disclosure of the present invention as long as the combination does not depart from the spirit of the present invention.
Claims (3)
1. A polylactic acid-polyethylene glycol succinate copolymer is characterized in that: the structural general formula of the polylactic acid-polyethylene glycol succinate copolymer is as follows:
wherein m and n are polymerization degrees of polymerization units, and are the same or different and are natural integers; the weight average molecular weight of the copolymer is between 50100 and 78500.
2. The method for preparing the polylactic acid-polyethylene glycol succinate copolymer according to claim 1, wherein the method comprises the following steps: the preparation method of the polylactic acid-poly (ethylene succinate) copolymer comprises the following steps of:
(1) synthesizing prepolymer polyethylene glycol succinate:
mixing ethylene glycol and succinic acid according to a molar ratio of 1.08-1.55: 1, adding the catalyst into a reaction kettle according to the mass ratio, keeping the system pressure at 0.20-0.30MPa at the temperature of 110-195 ℃ in an inert atmosphere, reacting for 4-8 hours until no small molecular fraction is evaporated, vacuumizing the obtained esterification reaction product to control the vacuum degree within 200Pa, reacting for 2-8 hours at the temperature of 170-200 ℃, and performing vacuum extrusion to obtain the poly (ethylene succinate) prepolymer;
(2) and (3) synthesis of polylactic acid-polyethylene glycol succinate copolymer:
in a reaction kettle, the mass ratio of 1-3.15: 1, adding an L-lactide and poly (ethylene succinate) prepolymer, then adding a catalyst, wherein the content of the L-lactide is 0.5-1.2 mol%, heating to 125-200 ℃ in an inert atmosphere, and reacting for 12-24 hours to obtain a poly (lactic acid-poly (ethylene succinate) copolymer;
(3) post-treatment of the copolymer:
and (3) dissolving the polylactic acid-polyethylene glycol succinate copolymer obtained in the step (2) by using chloroform, precipitating by using absolute ethyl alcohol, and drying in vacuum at 40-50 ℃ to obtain the polylactic acid-polyethylene glycol succinate copolymer.
3. The method for preparing the polylactic acid-polyethylene glycol succinate copolymer according to claim 2, wherein the method comprises the following steps: the catalyst is a catalyst for common esterification reaction, and more preferably any one or two of tin dioctoate, antimony trioxide, tin oxide, tetrabutyl titanate, tetrapropyl titanate and polyphosphoric acid.
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| CN202111465001.XA Pending CN113999373A (en) | 2021-12-03 | 2021-12-03 | Polylactic acid-polyethylene glycol succinate copolymer and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101134807A (en) * | 2007-10-25 | 2008-03-05 | 上海同杰良生物材料有限公司 | Polylactic acid radical biological degradable material and method for preparing same |
| CN102786672A (en) * | 2012-08-29 | 2012-11-21 | 中国科学院长春应用化学研究所 | Preparation method of polylactic acid segmented copolymer |
| CN103788379A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Modified polyethylene glycol succinate and preparation methods thereof |
| CN104592503A (en) * | 2013-10-30 | 2015-05-06 | 中国石油化工股份有限公司 | Polylactic acid ternary block copolyester and preparation method thereof |
| CN105418900A (en) * | 2016-01-12 | 2016-03-23 | 中国科学院长春应用化学研究所 | Preparation methods of butylene succinate and polylactic acid segmented copolymer |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134807A (en) * | 2007-10-25 | 2008-03-05 | 上海同杰良生物材料有限公司 | Polylactic acid radical biological degradable material and method for preparing same |
| CN102786672A (en) * | 2012-08-29 | 2012-11-21 | 中国科学院长春应用化学研究所 | Preparation method of polylactic acid segmented copolymer |
| CN103788379A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Modified polyethylene glycol succinate and preparation methods thereof |
| CN104592503A (en) * | 2013-10-30 | 2015-05-06 | 中国石油化工股份有限公司 | Polylactic acid ternary block copolyester and preparation method thereof |
| CN105418900A (en) * | 2016-01-12 | 2016-03-23 | 中国科学院长春应用化学研究所 | Preparation methods of butylene succinate and polylactic acid segmented copolymer |
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