CN113388094A - Toughening agent, toughened polylactic acid and preparation method thereof - Google Patents
Toughening agent, toughened polylactic acid and preparation method thereof Download PDFInfo
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- CN113388094A CN113388094A CN202110657364.7A CN202110657364A CN113388094A CN 113388094 A CN113388094 A CN 113388094A CN 202110657364 A CN202110657364 A CN 202110657364A CN 113388094 A CN113388094 A CN 113388094A
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- 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
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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Abstract
The invention relates to the technical field of degradable materials, and particularly discloses a toughening agent, a toughened polylactic acid and a preparation method thereof, wherein the preparation method of the toughening agent comprises the following steps: the polylactic acid is prepared by taking 30-60 mole parts of lactic acid, 5-10 mole parts of itaconic acid and 40-70 mole parts of a mixture of dicarboxylic acid and dihydric alcohol and carrying out polycondensation reaction. The toughened polylactic acid is prepared from the toughening agent. The toughening agent can realize good toughening effect, has high degradation rate, has no harm to human bodies/soil and the like due to degradation products, has good toughening effect and has full degradation characteristic.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of degradable materials, in particular to a toughening agent, a toughened polylactic acid and a preparation method thereof.
[ background of the invention ]
Plastics are high molecular compounds obtained by polymerization of monomers by addition polymerization or polycondensation, which have a moderate deformation resistance between fibers and rubber, and are composed of synthetic resin, fillers, plasticizers, stabilizers, lubricants, colorants, and other additives. Plastics relate to a plurality of fields such as packing, medicine, chemical industry, life, agriculture, etc., and plastic products are also various, including packaging bags, plastic films, disposable tableware, plastic bottles, foamed plastic fillers, articles for daily use, etc.
Because of the use of a large amount of plastics, plastic wastes are more and more, so that white pollution is more and more serious, pollution and harm are brought to the natural environment, the existing plastic raw materials such as polypropylene, polyethylene, polystyrene, polyvinyl chloride, polyethylene terephthalate and the like belong to non-degradable plastic materials and can be treated only by recovery and burying, but the existing plastic recovery classification is complex, the cost is high, the recovery is difficult, the recovery amount is low, and due to the non-degradability of the plastic, the plastic can be completely degraded in hundreds of years after being buried, the plastic occupies the land for a long time, influences the soil quality and causes long-term and deep ecological environment problems.
In order to reduce white pollution, the existing plastic raw materials gradually develop towards the degradable direction, and partially degradable materials such as starch-based polypropylene and the like appear, but the materials can only realize partial degradation and cannot realize complete degradation. With the development of technology, fully degradable materials come out gradually and develop rapidly, wherein polylactic acid is a fully degradable plastic product with the largest production energy and the most mature industrial chain, but the application of polylactic acid is limited due to the defects of product performance caused by the problems of overlarge brittleness, lower breaking elongation and impact strength and the like, so a great deal of research is made on toughening modification of polylactic acid, and the physical blending method of adding a toughening agent is mainly used at present.
The existing toughening agent has poor compatibility with polylactic acid due to the limitation of materials and processes, so that the toughening effect is limited, or the dosage of the toughening agent is large, so that the manufacturing cost is high, and the toughening agent mainly takes inorganic and non-degradable organic materials (simultaneously, petroleum-based materials), so that the renewable source and the full-degradation characteristic of the polylactic acid are damaged, and the full degradation of plastics is not facilitated.
[ summary of the invention ]
In order to solve the technical problem of high plastic degradation difficulty in the prior art, the invention provides a toughening agent, a toughened polylactic acid and a preparation method thereof.
The invention provides a preparation method of a toughening agent, which comprises the following steps: the polylactic acid is prepared by taking 30-60 mole parts of lactic acid, 5-10 mole parts of itaconic acid and 40-70 mole parts of a mixture of dicarboxylic acid and dihydric alcohol and carrying out polycondensation reaction.
Preferably, the polycondensation reaction is carried out in an inert environment, comprising at least the following steps: mixing lactic acid, itaconic acid and a mixture of dicarboxylic acid and dihydric alcohol, reacting for 1.5-3.5h at 100-130 ℃ under normal pressure, and pre-esterifying; reacting for 1.5-3.5h at 160-; the reaction is carried out for 4 to 8 hours at the temperature of 200 ℃ and 240 ℃ and under the condition of 10 to 30KPa for polycondensation, thus obtaining the toughening agent.
Preferably, the toughening agent is purified by using an organic solvent and an alcohol compound, wherein the volume ratio of the organic solvent to the alcohol compound is 1 (1.5-3).
Preferably, the organic solvent comprises at least one of chloroform and tetrahydrofuran, and/or the alcohol compound comprises at least one of methanol and ethanol.
Preferably, the molar ratio of diol to dicarboxylic acid in the mixture of diol and dicarboxylic acid is (1-1.5): 1.
Preferably, the diol comprises at least one of butanediol, propanediol, hexanediol, and/or the dicarboxylic acid comprises at least one of sebacic acid, succinic acid, adipic acid, 2, 5-furandicarboxylic acid.
Preferably, the dicarboxylic acid comprises a mixture of sebacic acid and succinic acid in a molar ratio of (0.3-4): 1.
In order to further solve the technical problems, the invention also provides a toughening agent which is prepared according to the preparation method of the toughening agent.
In order to further solve the technical problems, the invention also provides a preparation method of the toughened polylactic acid, which comprises the steps of carrying out blending reaction on the toughened raw material and the polylactic acid according to the mass ratio of 1/20-1/5, wherein the blending temperature is 200-260 ℃, and the blending time is 5-20 min; wherein the toughening raw material is the toughening agent of claim 8.
In order to further solve the technical problems, the invention also provides toughened polylactic acid which is prepared according to the preparation method of the toughened polylactic acid.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1. the preparation method of the toughening agent has the advantages of simple process and low cost, and the prepared toughening agent has the effects of no harm, good toughening effect and full degradability.
2. The mixture of the dihydric alcohol and the dicarboxylic acid is prepared by mixing the dihydric alcohol and the dicarboxylic acid with the molar ratio of (1-1.5):1, so that the polymerization effect can be further improved, and the toughening capability is optimized.
3. The toughening agent can realize good toughening effect, has high degradation rate, has no harm to human bodies, soil and the like due to degradation products, has good toughening effect and has full degradation characteristic.
4. The preparation method of the toughened polylactic acid has simple flow and low cost, and the prepared toughened polylactic acid has good toughness, no harm and full degradation characteristic.
5. The toughening polylactic acid toughening agent has low content and manufacturing cost, high toughness and full degradation characteristic, high degradation rate, and no harm to the degraded product, and belongs to full degradation safety materials.
[ description of the drawings ]
FIG. 1 is a schematic flow diagram of a process for preparing the toughening agent of the present invention;
FIG. 2 is a schematic flow diagram of the polycondensation reaction in the process for making the toughener of the present invention;
FIG. 3 is a strain graph of an experimental group and a control group according to the present invention;
FIG. 4 is a bar graph of the impact strength of the experimental group and the control group of the present invention;
FIG. 5 is a graph showing the degradation rates of the experimental group and the control group of the present invention.
[ detailed description ] embodiments
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Reference in the specification to "one embodiment," "a preferred embodiment," "an embodiment," or "embodiments" means that a particular feature, structure, characteristic, or function described in connection with the embodiment is included in at least one embodiment of the invention and may be in more than one embodiment. The appearances of the phrases "in one embodiment," "in an embodiment," or "in various embodiments" in various places in the specification are not necessarily all referring to the same embodiment or embodiments.
The invention provides a toughening agent which comprises the following raw materials in parts by mole: 30-60 parts of lactic acid; 5-10 parts of itaconic acid; and 40-70 parts of a mixture of dihydric alcohol and dicarboxylic acid.
The toughening agent can realize good toughening effect, has high degradation rate, has no harm to human bodies, soil and the like due to degradation products, has good toughening effect and has full degradation characteristic.
In order to further improve the polymerization effect of the toughening agent and optimize the toughening capability, the raw materials of the mixture of the dihydric alcohol and the dicarboxylic acid comprise the dihydric alcohol and the dicarboxylic acid with the molar ratio of (1-1.5): 1. Alternatively, the starting material for the mixture of diols and dicarboxylic acids may also comprise a molar ratio of 1.1: 1. 1.2: 1. 1.3: 1. 1.4:1, etc., and is not limited thereto.
In order to optimize the polymerization effect and improve the polymerization efficiency, the dihydric alcohol comprises at least one of butanediol, propanediol and hexanediol. The dicarboxylic acid comprises at least one of sebacic acid, succinic acid, adipic acid and 2, 5-furandicarboxylic acid.
The dicarboxylic acid comprises a mixture of sebacic acid and succinic acid in a molar ratio of (0.3-4): 1. Alternatively, the molar ratio of sebacic acid to succinic acid may also be 0.5: 1. 0.8: 1.1: 1. 1.2: 1. 1.5: 1.2: 1. 2.5: 1.3: 1. 3.5: 1.4:1, etc., and is not limited thereto.
Referring to fig. 1, the present invention further provides a method for preparing a toughening agent, comprising the following steps:
s1, taking 30-60 mole parts of lactic acid, 5-10 mole parts of itaconic acid and 40-70 mole parts of a mixture of dicarboxylic acid and dihydric alcohol; and
s2, preparing the toughening agent through polycondensation.
Referring to fig. 2, the polycondensation reaction in step S2 at least includes the following steps:
s21, mixing lactic acid, itaconic acid and a mixture of dicarboxylic acid and dihydric alcohol, reacting at 100-130 ℃ for 1.5-3.5h under normal pressure, and pre-esterifying;
s22, after the pre-esterification is finished, reacting for 1.5-3.5h at the temperature of 160-200 ℃ under normal pressure, and carrying out esterification dehydration;
s23, after esterification and dehydration, the mixture reacts for 4 to 8 hours at the temperature of 200 ℃ and 240 ℃ under the condition of 10 to 30KPa for polycondensation to obtain a substance to be purified;
s24, purifying the object to be purified to obtain the toughening agent.
Purifying the substance to be purified by using an organic solvent and an alcohol compound, wherein the volume ratio of the organic solvent to the alcohol compound is 1 (1.5-3), and optionally, the volume ratio of the organic solvent to the alcohol compound can also be 1:1.7, 1: 1.8, 1:2. 1: 2.2, 1:2.5, 1:2.8, etc., and is not limited thereto.
In order to improve the purification effect and the purification efficiency, the organic solvent comprises at least one of chloroform and tetrahydrofuran, and the alcohol compound comprises at least one of methanol and ethanol.
In order to ensure the purity of the product, the pre-esterification, the esterification dehydration and the polycondensation are carried out in a nitrogen atmosphere.
In order to more clearly describe the technical solution of the present invention, the following description is made with reference to specific embodiments.
Example 1
The embodiment provides a toughening agent, and the raw materials of the toughening agent comprise: 30 mole parts of lactic acid, 5 mole parts of itaconic acid, and 40 mole parts of a dicarboxylic acid and diol mixture. The toughening agent is prepared from the raw materials.
Wherein the mixture of the dihydric alcohol and the dicarboxylic acid is formed by mixing butanediol and sebacic acid with the molar ratio of 1:1.
Example 2
The embodiment provides a toughening agent, and the raw materials of the toughening agent comprise: 35 mole parts of lactic acid, 5 mole parts of itaconic acid, and 45 mole parts of a dicarboxylic acid and diol mixture. The toughening agent is prepared from the raw materials.
Wherein the mixture of the dihydric alcohol and the dicarboxylic acid is prepared by mixing propylene glycol and succinic acid with the molar ratio of 1.1: 1.
Example 3
The embodiment provides a toughening agent, and the raw materials of the toughening agent comprise: 40 mole parts of lactic acid, 6 mole parts of itaconic acid, and 50 mole parts of a dicarboxylic acid and diol mixture. The toughening agent is prepared from the raw materials.
Wherein the mixture of the dihydric alcohol and the dicarboxylic acid is formed by mixing hexanediol and adipic acid with a molar ratio of 1.2: 1.
Example 4
The embodiment provides a toughening agent, and the raw materials of the toughening agent comprise: 45 mole parts of lactic acid, 7 mole parts of itaconic acid, and 55 mole parts of a dicarboxylic acid and diol mixture. The toughening agent is prepared from the raw materials.
Wherein the mixture of the dihydric alcohol and the dicarboxylic acid is formed by mixing hexanediol and adipic acid with a molar ratio of 1.3: 1.
Example 5
The embodiment provides a toughening agent, and the raw materials of the toughening agent comprise: 50 mole parts of lactic acid, 8 mole parts of itaconic acid, and 60 mole parts of a dicarboxylic acid and diol mixture. The toughening agent is prepared from the raw materials.
Wherein the mixture of the dihydric alcohol and the dicarboxylic acid is formed by mixing hexanediol and 2, 5-furandicarboxylic acid with a molar ratio of 1.4: 1.
Example 6
The embodiment provides a toughening agent, and the raw materials of the toughening agent comprise: 55 mole parts of lactic acid, 9 mole parts of itaconic acid, and 65 mole parts of a dicarboxylic acid and diol mixture. The toughening agent is prepared from the raw materials.
Wherein, the dihydric alcohol is a mixture of butanediol and propanediol, the dicarboxylic acid is a mixture of sebacic acid and succinic acid with a molar ratio of 1:1, and the molar ratio of the dihydric alcohol to the dicarboxylic acid is 1.5: 1.
Example 7
The embodiment provides a toughening agent, and the raw materials of the toughening agent comprise: 60 mole parts of lactic acid, 10 mole parts of itaconic acid, and 70 mole parts of a dicarboxylic acid and diol mixture. The toughening agent is prepared from the raw materials.
Wherein, the dihydric alcohol is a mixture of propylene glycol and hexanediol, the dicarboxylic acid is a mixture of succinic acid and adipic acid with a molar ratio of 1:1, and the molar ratio of the dihydric alcohol to the dicarboxylic acid is 1.1: 1.
Example 8
The embodiment provides a toughening agent, and the raw materials of the toughening agent comprise: 60 mole parts of lactic acid, 10 mole parts of itaconic acid, and 70 mole parts of a dicarboxylic acid and diol mixture. The toughening agent is prepared from the raw materials.
Wherein, the dihydric alcohol is a mixture of propylene glycol and hexanediol, the dicarboxylic acid is a mixture of succinic acid and adipic acid with a molar ratio of 1:1, and the molar ratio of the dihydric alcohol to the dicarboxylic acid is 1.1: 1.
Example 9
The embodiment provides a toughening agent, and the raw materials of the toughening agent comprise: 60 mole parts of lactic acid, 10 mole parts of itaconic acid, and 70 mole parts of a dicarboxylic acid and diol mixture. The toughening agent is prepared from the raw materials.
Wherein, the dihydric alcohol is a mixture of propylene glycol and hexanediol, the dicarboxylic acid is a mixture of succinic acid and adipic acid with a molar ratio of 1:1, and the molar ratio of the dihydric alcohol to the dicarboxylic acid is 1.1: 1.
Example 10
The embodiment provides a preparation method of a toughening agent, which comprises the following steps:
mixing the raw materials of the toughening agent in the embodiment 1, placing the mixture at 100 ℃ and reacting for 1.5h under normal pressure, and pre-esterifying;
after the pre-esterification is finished, the reaction is carried out for 1.5h at the temperature of 160 ℃ and under the normal pressure, and esterification dehydration is carried out;
after esterification and dehydration, the mixture reacts for 4 hours at 200 ℃ and 10KPa to carry out polycondensation, and a substance to be purified is obtained;
and (3) dissolving the substance to be purified in trichloromethane, and adding methanol at 0 ℃ for purification to obtain the toughening agent 1.
Wherein, the pre-esterification, the esterification dehydration and the polycondensation are all carried out in the nitrogen atmosphere, and the volume ratio of the trichloromethane to the methanol is 1: 1.5.
Example 11
The embodiment provides a preparation method of a toughening agent, which comprises the following steps:
mixing the raw materials of the toughening agent in the embodiment 2, reacting for 1.8h at 105 ℃ under normal pressure after mixing, and pre-esterifying;
after the pre-esterification is finished, the mixture reacts for 1.8h at 165 ℃ under normal pressure, and esterification dehydration is carried out;
after esterification and dehydration, the mixture reacts for 4.5 hours at 205 ℃ and 13KPa to carry out polycondensation, thus obtaining a substance to be purified;
and (3) dissolving the substance to be purified in trichloromethane, and adding methanol at 0 ℃ for purification to obtain the toughening agent 2.
Wherein, the pre-esterification, the esterification dehydration and the polycondensation are all carried out in the nitrogen atmosphere, and the volume ratio of the trichloromethane to the methanol is 1: 1.5.
Example 12
The embodiment provides a preparation method of a toughening agent, which comprises the following steps:
mixing the raw materials of the toughening agent in the embodiment 3, placing the mixture at 110 ℃ and reacting for 2.1h under normal pressure, and pre-esterifying;
after the pre-esterification is finished, reacting for 2.1h at 170 ℃ under normal pressure, and carrying out esterification dehydration;
after esterification and dehydration, the mixture reacts for 5 hours at 210 ℃ and 16KPa to carry out polycondensation, and a substance to be purified is obtained;
and (3) dissolving the substance to be purified in trichloromethane, and adding methanol at 0 ℃ for purification to obtain the toughening agent 3.
Wherein, the pre-esterification, the esterification dehydration and the polycondensation are all carried out in the nitrogen atmosphere, and the volume ratio of the trichloromethane to the methanol is 1: 1.7.
Example 13
The embodiment provides a preparation method of a toughening agent, which comprises the following steps:
mixing the raw materials of the toughening agent in the embodiment 4, reacting for 2.4h at 115 ℃ under normal pressure after mixing, and pre-esterifying;
after the pre-esterification is finished, the mixture reacts for 2.4 hours at the temperature of 175 ℃ and under normal pressure, and esterification dehydration is carried out;
after esterification and dehydration, the mixture reacts for 5.5 hours at 215 ℃ and 21KPa to carry out polycondensation, thus obtaining a substance to be purified;
and (3) dissolving the substance to be purified in trichloromethane, and adding methanol at 0 ℃ for purification to obtain the toughening agent 4.
Wherein, the pre-esterification, the esterification dehydration and the polycondensation are all carried out in the nitrogen atmosphere, and the volume ratio of the trichloromethane to the methanol is 1: 1.9.
Example 14
The embodiment provides a preparation method of a toughening agent, which comprises the following steps:
mixing the raw materials of the toughening agent in the embodiment 5, reacting for 2.7h at 120 ℃ under normal pressure after mixing, and pre-esterifying;
after the pre-esterification is finished, reacting for 2.7h at 180 ℃ under normal pressure, and carrying out esterification dehydration;
after esterification and dehydration, the mixture reacts for 6 hours at 220 ℃ and 24KPa for polycondensation to obtain a substance to be purified;
and (3) dissolving the substance to be purified in trichloromethane, and adding methanol at 0 ℃ for purification to obtain the toughening agent 5.
Wherein, the pre-esterification, the esterification dehydration and the polycondensation are all carried out in the nitrogen atmosphere, and the volume ratio of the trichloromethane to the methanol is 1: 2.1.
Example 15
The embodiment provides a preparation method of a toughening agent, which comprises the following steps:
mixing the raw materials of the toughening agent in the embodiment 6, reacting for 3 hours at 125 ℃ under normal pressure, and pre-esterifying;
after the pre-esterification is finished, reacting for 3 hours at 185 ℃ under normal pressure, and carrying out esterification dehydration;
after esterification and dehydration, the mixture reacts for 6.5 hours at 225 ℃ and 27KPa for polycondensation to obtain a substance to be purified;
and (3) dissolving the substance to be purified in trichloromethane, and adding methanol at 0 ℃ for purification to obtain the toughening agent 6.
Wherein, the pre-esterification, the esterification dehydration and the polycondensation are all carried out in the nitrogen atmosphere, and the volume ratio of the trichloromethane to the methanol is 1: 2.3.
Example 16
The embodiment provides a preparation method of a toughening agent, which comprises the following steps:
mixing the raw materials of the toughening agent in the embodiment 7, placing the mixture at 130 ℃ and reacting for 3.2h under normal pressure, and pre-esterifying;
after the pre-esterification is finished, reacting for 3.2 hours at 190 ℃ under normal pressure, and carrying out esterification dehydration;
after esterification and dehydration, the mixture reacts for 7 hours at 230 ℃ and 30KPa for polycondensation to obtain a substance to be purified;
and (3) dissolving the substance to be purified in trichloromethane, and adding methanol at 0 ℃ for purification to obtain the toughening agent 7.
Wherein, the pre-esterification, the esterification dehydration and the polycondensation are all carried out in the nitrogen atmosphere, and the volume ratio of the trichloromethane to the methanol is 1: 2.5.
Example 17
The embodiment provides a preparation method of a toughening agent, which comprises the following steps:
mixing the raw materials of the toughening agent in the embodiment 8, placing the mixture at 130 ℃ and reacting for 3.2h under normal pressure, and pre-esterifying;
after the pre-esterification is finished, the mixture reacts for 3.5 hours at the temperature of 195 ℃ and under the normal pressure condition, and esterification dehydration is carried out;
after esterification and dehydration, the mixture reacts for 7.5 hours at 235 ℃ and 30KPa for polycondensation to obtain a substance to be purified;
and (3) dissolving the substance to be purified in trichloromethane, and adding methanol at 0 ℃ for purification to obtain the toughening agent 8.
Wherein, the pre-esterification, the esterification dehydration and the polycondensation are all carried out in the nitrogen atmosphere, and the volume ratio of the trichloromethane to the methanol is 1: 2.8.
Example 18
The embodiment provides a preparation method of a toughening agent, which comprises the following steps:
mixing the raw materials of the toughening agent in the embodiment 9, placing the mixture at 130 ℃ and reacting for 3.2h under normal pressure, and pre-esterifying;
after the pre-esterification is finished, reacting for 3.5 hours at 200 ℃ under normal pressure, and carrying out esterification dehydration;
after esterification and dehydration, the mixture reacts for 8 hours at the temperature of 240 ℃ and under the condition of 30KPa to carry out polycondensation, and a substance to be purified is obtained;
and (3) dissolving the substance to be purified in trichloromethane, and adding methanol at 0 ℃ for purification to obtain the toughening agent 9.
Wherein, the pre-esterification, the esterification dehydration and the polycondensation are all carried out in the nitrogen atmosphere, and the volume ratio of the trichloromethane to the methanol is 1: 3.
Example 19
The embodiment provides a toughened polylactic acid, which comprises the following raw materials: polylactic acid, and the resulting toughener prepared in any of example 10, example 11, and example 12. Wherein the mass ratio of the toughening agent to the polylactic acid is 1: 20.
example 20
The embodiment provides a toughened polylactic acid, which comprises the following raw materials: polylactic acid, and the resulting toughener prepared in any of example 13, example 14, and example 15. Wherein the mass ratio of the toughening agent to the polylactic acid is 1: 10.
example 21
The embodiment provides a toughened polylactic acid, which comprises the following raw materials: polylactic acid, and the resulting toughener prepared in either of examples 16 and 17. Wherein the mass ratio of the toughening agent to the polylactic acid is 3: 20.
example 22
The embodiment provides a toughened polylactic acid, which comprises the following raw materials: polylactic acid, and the toughener prepared in example 18. Wherein the mass ratio of the toughening agent to the polylactic acid is 1: 5.
example 23
The embodiment provides a preparation method of toughened polylactic acid, which comprises the following steps: the raw materials of the toughened polylactic acid in the embodiment 19 are mixed and then are subjected to blending reaction at the blending temperature of 230 ℃ for 10min, so that the toughened polylactic acid 1, the toughened polylactic acid 2 and the toughened polylactic acid 3 are respectively obtained.
Wherein, the toughening agent of the embodiment 10 correspondingly toughens the polylactic acid 1, the toughening agent of the embodiment 11 correspondingly toughens the polylactic acid 2, and the toughening agent of the embodiment 12 correspondingly toughens the polylactic acid 3.
Example 24
The embodiment provides a preparation method of toughened polylactic acid, which comprises the following steps: the raw materials of the toughened polylactic acid in the embodiment 20 are mixed and then are subjected to blending reaction at the blending temperature of 230 ℃ for 10min, so that the toughened polylactic acid 4, the toughened polylactic acid 5 and the toughened polylactic acid 6 are respectively obtained.
Wherein, the toughening agent of the embodiment 13 is corresponding to toughening polylactic acid 4, the toughening agent of the embodiment 14 is corresponding to toughening polylactic acid 5, and the toughening agent of the embodiment 15 is corresponding to toughening polylactic acid 6.
Example 25
The embodiment provides a preparation method of toughened polylactic acid, which comprises the following steps: the raw materials of the toughened polylactic acid in the embodiment 21 are mixed and then are subjected to blending reaction at the blending temperature of 230 ℃ for 10min, so that the toughened polylactic acid 7 and the toughened polylactic acid 8 are respectively obtained.
Wherein, the toughening agent of the embodiment 16 correspondingly toughens the polylactic acid 7, and the toughening agent of the embodiment 17 correspondingly toughens the polylactic acid 8.
Example 26
The embodiment provides a preparation method of toughened polylactic acid, which comprises the following steps: the raw materials of the toughened polylactic acid in the embodiment 22 are mixed and then are subjected to blending reaction at the blending temperature of 230 ℃ for 10min, so that the toughened polylactic acid 9 is obtained. Wherein the toughening agent of example 18 correspondingly toughens polylactic acid 9,
control group 1
Taking polylactic acid with the toughening agent content of 0 as pure polylactic acid of a reference.
Control group 2
The toughening agent prepared by the preparation method of example 10 was used as a control pure toughening agent without adding polylactic acid.
And selecting toughened polylactic acid 1, toughened polylactic acid 4, toughened polylactic acid 7 and toughened polylactic acid 9 as experimental groups, and carrying out control experiments with a control group 1 and a control group 2. As shown in fig. 3 to 5:
FIG. 3 is a Strain graph in which the abscissa Strain (%) represents Strain, the ordinate stress (mpa) represents stress, and the curves A to E represent Strain curves of the pure polylactic acids of toughened polylactic acid 1, toughened polylactic acid 4, toughened polylactic acid 7, toughened polylactic acid 9, and control 1, respectively. As is known, when the end point of the strain curve is a breaking point, the stress and strain corresponding to the end point are the tensile strength (breaking strength) and breaking elongation of the corresponding material, respectively, and are the ultimate strength and ultimate elongation at which the corresponding material breaks.
Based on this, as shown in fig. 3, the elongation at break of the pure polylactic acid of control 1 is only about 10%, the elongation at break of toughened polylactic acid 1 is about 95%, the elongation at break of toughened polylactic acid 4 is about 170%, the elongation at break of toughened polylactic acid 7 is about 320%, and the elongation at break of toughened polylactic acid 9 is about 230%.
Thus, it can be seen that: the pure polylactic acid of the control group 1 has lower elongation at break, and the elongation at break of the toughened polylactic acid 1, the toughened polylactic acid 4, the toughened polylactic acid 7 and the toughened polylactic acid 9 is obviously increased along with the addition of the toughening agent, which indicates that the addition of the toughening agent effectively improves the elongation at break of the polylactic acid, and the addition of the toughening agent in the polylactic acid also improves the toughness of the polylactic acid because the elongation at break is an index for measuring the toughness.
In the toughening polylactic acid 7, when the mass ratio of the toughening agent to the polylactic acid is 3: the elongation at break of the toughened polylactic acid formed at 20 hours is improved most obviously, the elongation at break is integrally improved to 320 percent, which is 50 times of the original length, and the mass ratio of the toughening agent to the polylactic acid in the toughened polylactic acid 7 is more ideal.
It can be further shown that the toughening agent of the invention has good toughening effect (elongation at break), and the dosage of the toughening agent is low, so that the toughening cost is not increased. And because of adding the toughening agent, the toughened polylactic acid prepared by the invention also has the characteristics of good toughness, low content of the toughening agent and low manufacturing cost.
Fig. 4 is a bar graph of Impact Strength corresponding to the pure polylactic acids of toughened polylactic acid 1, toughened polylactic acid 4, toughened polylactic acid 7, toughened polylactic acid 9 and comparison group 1, wherein PLBSI content (wt%) represents the content of the toughening agent, ordinate Impact Strength (KJ/square meter) represents the Impact Strength, and vertical columns a-E in the figure represent the Impact Strength of the pure polylactic acids of toughened polylactic acid 1, toughened polylactic acid 4, toughened polylactic acid 7, toughened polylactic acid 9 and comparison group 1 respectively.
Based on this, as shown in fig. 4, the impact strength of the pure polylactic acid of the comparison group 1 is only 2.7 KJ/square meter, the impact strength of the toughened polylactic acid 1 is 7 KJ/square meter, the impact strength of the toughened polylactic acid 4 is 17.5 KJ/square meter, the impact strength of the toughened polylactic acid 7 is 35.7 KJ/square meter, and the impact strength of the toughened polylactic acid 9 is 8.5 KJ/square meter.
Thus, it can be seen that: the impact strength of the pure polylactic acid of the control group 1 is lower, the impact strength of the toughened polylactic acid 1, the toughened polylactic acid 4, the toughened polylactic acid 7 and the toughened polylactic acid 9 is obviously increased along with the addition of the toughening agent, which shows that the impact strength of the polylactic acid is effectively improved by the addition of the toughening agent.
In the toughening polylactic acid 7, when the mass ratio of the toughening agent to the polylactic acid is 3: the impact strength of the toughened polylactic acid formed at 20 hours is improved most obviously, the whole impact strength is improved to 35.7 KJ/square meter which is 15 times of the original impact strength, and the mass ratio of the toughening agent corresponding to the toughened polylactic acid 7 to the polylactic acid is more ideal.
It can be further shown that the toughening agent of the invention has good toughening effect (impact strength), and the dosage of the toughening agent is low, so that the toughening cost cannot be increased. And because of adding the toughening agent, the toughened polylactic acid prepared by the invention also has the characteristics of good toughness, low content of the toughening agent and low manufacturing cost.
FIG. 5 is a graph showing degradation rates of the pure polylactic acids of toughened polylactic acid 1, toughened polylactic acid 4, toughened polylactic acid 7, toughened polylactic acid 9, comparative group 1 and the pure toughening agents of comparative group 2, wherein the abscissa time (day) represents time, the ordinate Weight (%) represents Weight, and the curves A to F respectively show degradation curves of the pure polylactic acids of toughened polylactic acid 1, toughened polylactic acid 4, toughened polylactic acid 7, toughened polylactic acid 9, comparative group 1 and the pure toughening agents of comparative group 2.
Based on this, as shown in fig. 5, the degradation rate of the pure polylactic acid of the control group 1 is the highest within 30 days, and is degraded by more than 55%; the degradation rate of the pure toughening agent of the control group 2 is the lowest within 30 days, and only about 35 percent of the pure toughening agent is degraded; the degradation amount of the toughened polylactic acid 1 in 30 days is about 50 percent; the degradation amount of the toughened polylactic acid 4 in 30 days is about 48 percent; the degradation amount of the toughened polylactic acid 7 in 30 days is about 45 percent; the degradation amount of the toughened polylactic acid 9 in 30 days is about 40 percent.
Thus, it can be seen that: the degradation rate of the pure polylactic acid of the control group 1 is the highest, the degradation rate of the pure toughening agent of the control group 2 is the lowest, and the degradation rates of the toughened polylactic acid 1, the toughened polylactic acid 4, the toughened polylactic acid 7 and the toughened polylactic acid 9 are all reduced relative to the degradation rate of the pure polylactic acid with the addition of the toughening agent in the polylactic acid, but are all over 40 percent.
In the toughening polylactic acid 7, when the mass ratio of the toughening agent to the polylactic acid is 3: the degradation amount of the toughened polylactic acid formed at 20 hours is about 45%, and as can be seen from fig. 3 and 4, the reduction rate of the toughened polylactic acid is not significantly reduced in the ideal proportion, so the mass ratio of the toughening agent to the polylactic acid is 3: the toughened polylactic acid has high toughness and good degradation rate when the content is 20 hours.
It can be further demonstrated that the toughening agent of the invention has good degradability, and the degradation rate of polylactic acid is not obviously influenced due to the small addition amount. Meanwhile, the toughened polylactic acid has the characteristics of good toughness, low content of the toughening agent and low manufacturing cost, and also has good degradation effect and is comprehensively degraded.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1. the preparation method of the toughening agent has the advantages of simple process and low cost, and the prepared toughening agent has the effects of no harm, good toughening effect and full degradability.
2. The mixture of the dihydric alcohol and the dicarboxylic acid is prepared by mixing the dihydric alcohol and the dicarboxylic acid with the molar ratio of (1-1.5):1, so that the polymerization effect can be further improved, and the toughening capability is optimized.
3. The toughening agent can realize good toughening effect, has high degradation rate, has no harm to human bodies, soil and the like due to degradation products, has good toughening effect and has full degradation characteristic.
4. The preparation method of the toughened polylactic acid has simple flow and low cost, and the prepared toughened polylactic acid has good toughness, no harm and full degradation characteristic.
5. The toughening polylactic acid toughening agent has low content and manufacturing cost, high toughness and full degradation characteristic, high degradation rate, and no harm to the degraded product, and belongs to full degradation safety materials.
The above is the embodiment of the present invention. The foregoing is a preferred embodiment of the present invention, and the preferred embodiments in the preferred embodiments can be combined and used in any combination if not obviously contradictory or prerequisite to a certain preferred embodiment, and the specific parameters in the embodiments and examples are only for the purpose of clearly illustrating the invention verification process of the inventor and are not intended to limit the patent protection scope of the present invention, which is subject to the claims and the equivalent structural changes made by the content of the description and the drawings of the present invention are also included in the protection scope of the present invention.
Claims (10)
1. A method for preparing a toughening agent is characterized by comprising the following steps: the polylactic acid is prepared by taking 30-60 mole parts of lactic acid, 5-10 mole parts of itaconic acid and 40-70 mole parts of a mixture of dicarboxylic acid and dihydric alcohol and carrying out polycondensation reaction.
2. Process for the preparation of the toughening agent according to claim 1, wherein the polycondensation reaction is carried out in an inert environment, comprising at least the following steps:
mixing the lactic acid, the itaconic acid and the mixture of the dicarboxylic acid and the dihydric alcohol, reacting at 100-130 ℃ for 1.5-3.5h under normal pressure, and pre-esterifying;
reacting for 1.5-3.5h at 160-;
the reaction is carried out for 4 to 8 hours at the temperature of 200 ℃ and 240 ℃ and under the condition of 10 to 30KPa for polycondensation, thus obtaining the toughening agent.
3. The preparation method of the toughening agent according to claim 2, wherein the toughening agent is purified by using an organic solvent and an alcohol compound, and the volume ratio of the organic solvent to the alcohol compound is 1 (1.5-3).
4. The method of claim 3, wherein the organic solvent comprises at least one of chloroform and tetrahydrofuran, and/or the alcohol compound comprises at least one of methanol and ethanol.
5. The method for preparing the toughening agent according to claim 1, wherein the molar ratio of the dihydric alcohol to the dicarboxylic acid in the mixture of the dihydric alcohol and the dicarboxylic acid is (1-1.5): 1.
6. The method of claim 1, wherein the diol comprises at least one of butanediol, propanediol, hexanediol, and/or the dicarboxylic acid comprises at least one of sebacic acid, succinic acid, adipic acid, 2, 5-furandicarboxylic acid.
7. The method of claim 1, wherein the dicarboxylic acid comprises a mixture of sebacic acid and succinic acid in a molar ratio of (0.3-4): 1.
8. A toughening agent prepared according to the method for preparing the toughening agent of any one of claims 1 to 7.
9. A preparation method of toughened polylactic acid is characterized by comprising the following steps: carrying out blending reaction on the toughening raw material and the polylactic acid according to the mass ratio of 1/20-1/5, wherein the blending temperature is 200-260 ℃, and the blending time is 5-20 min;
wherein the toughening raw material is the toughening agent of claim 8.
10. The toughened polylactic acid is characterized by being prepared according to the preparation method of the toughened polylactic acid as claimed in claim 9.
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| CN116869950A (en) * | 2023-09-07 | 2023-10-13 | 药侠谷(北京)医药文化有限公司 | Blood pressure-reducing biodegradable subcutaneous implantation rod and preparation method thereof |
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| CN116869950A (en) * | 2023-09-07 | 2023-10-13 | 药侠谷(北京)医药文化有限公司 | Blood pressure-reducing biodegradable subcutaneous implantation rod and preparation method thereof |
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