CN113999507B - Shape memory thermoplastic elastomer material - Google Patents
Shape memory thermoplastic elastomer material Download PDFInfo
- Publication number
- CN113999507B CN113999507B CN202111334460.4A CN202111334460A CN113999507B CN 113999507 B CN113999507 B CN 113999507B CN 202111334460 A CN202111334460 A CN 202111334460A CN 113999507 B CN113999507 B CN 113999507B
- Authority
- CN
- China
- Prior art keywords
- parts
- silicon dioxide
- reaction
- stirring
- shape memory
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/12—Shape memory
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Abstract
The invention relates to a shape memory thermoplastic elastomer material, which belongs to the technical field of memory materials and comprises the following raw materials: 4-7 parts of styrene-ethylene-butylene-styrene block copolymer, 20-25 parts of styrene-butadiene-styrene block copolymer, 25-32 parts of plasticizer, 30-40 parts of polylactic acid, 1-3 parts of modified silicon dioxide, 5-7 parts of compatilizer and 1-2 parts of auxiliary agent; wherein, the modified silicon dioxide is prepared by the following steps: under the protection of nitrogen, mixing the epoxidized silicon dioxide, the carbodiimide modifier and the dimethyl sulfoxide, stirring for 10min at the temperature of 50-60 ℃, adding potassium hydroxide, carrying out reflux reaction for 3-5h, filtering, washing and drying to obtain modified silicon dioxide, and adding the modified silicon dioxide and the auxiliary agent to endow the polylactic acid shape memory thermoplastic elastomer material with good mechanical property, shape memory property, hydrolysis resistance and self-healing property.
Description
Technical Field
The invention belongs to the technical field of memory materials, and particularly relates to a shape memory thermoplastic elastomer material.
Background
Shape memory polymer materials (SMPs) are a novel intelligent polymer material with stimulus-response and have the characteristics of plastics and rubber. Compared with the traditional shape memory alloy, the SMPs have the characteristics of light weight, low price, large deformation amount, easy molding, easy shaping, convenient adjustment of recovery temperature and the like. The method is widely applied to the fields of aerospace industry, biomedicine, artificial intelligence, intelligent sensors and the like. In particular, the SMPs with good biocompatibility and biodegradability are novel functional materials with potential medical application, and have wide application prospects in the biomedical engineering fields of human body correction, thrombus prevention and treatment, surgical sutures, vascular stents, artificial bones, drug release and the like.
Polylactic acid (PLA) has high strength, modulus, excellent environmental friendliness and biocompatibility, and has become one of the most promising bio-based and biodegradable plastics. Thus, PLA can be used as a hard segment of a thermoplastic elastomer, and the overall properties of the elastomer can be controlled by changing the stereochemistry and crystallinity of the PLA segment. However, as a polyester material, PLA is not only poor in toughness, but also easily degraded by water molecules. Although hydrolysis of PLA is advantageous in some cases, such as after disposal of the PLA article to facilitate its rapid degradation to water and carbon dioxide, hydrolysis is in most cases a major drawback to PLA, such as during processing, storage and use of PLA, often resulting in a reduction in its performance.
Therefore, aiming at the problems of high hardness and poor hydrolysis resistance of the existing polylactic acid shape memory material, the technical problem to be solved at present is to provide a hydrolysis-resistant shape memory thermoplastic elastomer material.
Disclosure of Invention
The present invention aims to provide a shape memory thermoplastic elastomer material to solve the technical problems in the background art.
The purpose of the invention can be realized by the following technical scheme:
the shape memory thermoplastic elastomer material comprises the following raw materials in parts by weight: 4-7 parts of styrene-ethylene-butylene-styrene block copolymer (SEBS), 20-25 parts of styrene-butadiene-styrene block copolymer (SBS), 25-32 parts of plasticizer, 30-40 parts of polylactic acid, 1-3 parts of modified silicon dioxide, 5-7 parts of compatilizer and 1-2 parts of auxiliary agent;
the shape memory thermoplastic elastomer material is prepared by the following steps:
step one, adding a plasticizer, SEBS and SBS into a high-speed mixer, uniformly mixing, heating to 50 ℃, adding polylactic acid, modified silicon dioxide, a compatilizer and an auxiliary agent, keeping the temperature, stirring and mixing for 30min to obtain a mixture;
and secondly, transferring the mixture into a double-screw extruder, and performing melt extrusion and granulation to obtain the shape memory thermoplastic elastomer material, wherein the rotating speed of a screw is 25r/min, the feeding amount is 10kg/h, and the extrusion temperature is 180-200 ℃.
Further, the modified silica is prepared by the following steps:
step A1, adding chlorobenzene into a reaction kettle, introducing triphosgene, stirring for 20-30min under the condition that the rotation speed is 150-: 1, after the reaction is finished, introducing nitrogen to remove triphosgene and hydrogen chloride gas at the temperature of 80-85 ℃ to prepare an intermediate 1;
wherein the dosage ratio of chlorobenzene to 2-aminobenzol is 100-120 mL: 0.1mol, under the action of triphosgene, converting amino of 2-aminobenzyl alcohol into isocyanate group to obtain an intermediate 1, wherein the specific reaction process is as follows:
step A2, adding the intermediate 1, chlorobenzene and ethanol solution of sodium methoxide into a three-neck flask, refluxing, stirring and reacting for 7.5-8.5h, cooling after the reaction is finished, filtering, and distilling the filtrate to remove the chlorobenzene to obtain a carbodiimide modifier;
wherein the dosage ratio of the intermediate 1, chlorobenzene and sodium methoxide ethanol solution is 0.5 mol: 200 g: 10g of sodium methoxide ethanol solution is prepared by mixing sodium methoxide and absolute ethyl alcohol according to the mass ratio of 3: 10, under the catalytic action of sodium methoxide, the isocyanate of the intermediate 1 is condensed to generate carbodiimide to obtain the carbodiimide modifier, and the specific reaction process is as follows:
step A3, adding nano silicon dioxide, absolute ethyl alcohol and deionized water into a three-neck flask, performing ultrasonic dispersion for 20-40min at the frequency of 40-50kHz, then adding KH-560, stirring and reacting for 2-4h at room temperature and the rotation speed of 100-200r/min, after the reaction is finished, centrifuging for 10-15min at the rotation speed of 1000-1500r/min, washing the precipitate with deionized water for 3-5 times, and drying in an oven at the temperature of 60 ℃ to constant weight to obtain epoxidized silicon dioxide;
wherein the dosage ratio of the nano silicon dioxide, the absolute ethyl alcohol, the deionized water and the KH-560 is 2.5-3.2 g: 30mL of: 30mL of: 3.5-4.2mL, and carrying out surface modification on the nano silicon dioxide by using a coupling agent KH-560 to obtain epoxidized silicon dioxide;
step A4, under the protection of nitrogen, adding epoxidized silica, a carbodiimide modifier and dimethyl sulfoxide into a three-necked flask, controlling the temperature to be 50-60 ℃, stirring and reacting for 10min, then adding potassium hydroxide, carrying out reflux reaction for 3-5h, filtering after the reaction is finished, washing a filter cake with deionized water, and drying at 80 ℃ to obtain modified silica;
wherein, the dosage ratio of the epoxidized silica, the carbodiimide modifier, the dimethyl sulfoxide and the potassium hydroxide is 5.6-7.2 g: 1.7-2.4 g: 80-90 mL: 1.3-1.5g, and under the alkaline condition, the epoxy group of the epoxidized silica and the hydroxyl group of the carbodiimide modifier are subjected to ring-opening reaction to obtain the modified silica.
Further, the auxiliary agent is prepared by the following steps:
step B1, adding p-nitrobenzoic acid into a three-neck flask, slowly dripping a sodium hydroxide solution with the mass fraction of 12% into the three-neck flask, under an oil bath at 70 ℃, dripping a glucose aqueous solution with the mass fraction of 60% into the three-neck flask, cooling to 20 ℃ after dripping, stirring for reaction for 24 hours, dripping acetic acid to adjust the pH value to 6 after the reaction is finished, precipitating, filtering, washing a filter cake with deionized water for 3-5 times, and drying at 60 ℃ for 12 hours to obtain an azo compound;
wherein the dosage ratio of the p-nitrobenzoic acid, the sodium hydroxide solution and the glucose aqueous solution is 7 g: 110-120 mL: 100mL, taking nitrobenzoic acid as a reaction raw material to obtain an azo compound, wherein the structural formula of the azo compound is as follows:
step B2, adding an azo compound, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, p-toluenesulfonic acid, bis (2-hydroxyethyl) disulfide and toluene into a three-neck flask, heating to reflux, stirring, reacting for 4-6h, cooling to room temperature after the reaction is finished, adding a sodium bicarbonate solution with the concentration of 0.1mol/L to adjust the pH value to 7-8, separating liquid, drying an organic layer with anhydrous calcium chloride, and distilling under reduced pressure to obtain an auxiliary agent;
wherein the dosage ratio of the azo compound, the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, the bis (2-hydroxyethyl) disulfide and the toluene is 0.1 mol: 0.1 mol: 0.05 mol: 100mL, the dosage of the p-toluenesulfonic acid is 3-5% of the total mass of the azo compound, the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and the bis (2-hydroxyethyl) disulfide, and the azo compound, the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and the bis (2-hydroxyethyl) disulfide are subjected to esterification reaction under the catalytic action of the p-toluenesulfonic acid to obtain the auxiliary agent.
Further, the plasticizer is one or more of soybean oil, palm oil, castor oil, epoxidized soybean oil, cardanol and epoxidized cardanol acetate which are mixed according to any proportion.
Further, the compatilizer is one or more of glycidyl methacrylate grafted ethylene-butadiene block copolymer (SBS-g-GMA), glycidyl methacrylate grafted ethylene-vinyl acetate copolymer (EVA-g-GMA) and glycidyl methacrylate grafted styrene-ethylene-butadiene-styrene block copolymer (SEBS-g-GMA) which are mixed according to any proportion.
The invention has the beneficial effects that:
1. the invention provides a shape memory thermoplastic elastomer material which is obtained by melting, extruding and granulating raw materials of all components, has good toughness, an elastic phase styrene thermoplastic elastomer is added into a PLA material to form a dispersed phase, and PLA forms a continuous phase, so that the shape memory function of the PLA material is improved while the toughness of the material is improved.
2. The modified silicon dioxide is nano-scale silicon dioxide, when the content is low, the nano-scale silicon dioxide can reduce the crystallization of PLA molecular chains, the storage modulus and the mechanical property of the composite material are improved, the shape memory property is better, the modified silicon dioxide is grafted with a carbodiimide modifier, the carbodiimide modifier contains hydroxyl and carbodiimide groups, the carbodiimide groups can react with terminal carboxyl of polylactic acid to form a stable ureide structure, the hydrolytic resistance of the polylactic acid is improved, hydrogen bonding action can be formed between the hydroxyl and polylactic acid molecules, the crystallinity of the polylactic acid matrix is reduced, the toughness of the polylactic acid matrix is improved, and the shape memory thermoplastic elastomer material has higher elongation at break.
3. The auxiliary agent is obtained by carrying out esterification reaction on an azo compound, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and bis (2-hydroxyethyl) disulfide, wherein an azo group can generate cis-trans isomerism under the irradiation of ultraviolet light, so that a molecular structure is bent in space, physical crosslinking is formed between the auxiliary agent and an elastomer material through the action of a hydrogen bond, the hydrogen bond is broken when the auxiliary agent is heated, a reversible structure is formed, and the auxiliary agent contains a hindered phenol structure and a disulfide bond, so that the antioxidant and self-repairing performance can be endowed to the elastomer material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to 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. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This example provides a modified silica made by the steps of:
step A1, adding 100mL of chlorobenzene into a reaction kettle, introducing triphosgene, stirring for 20min at the rotation speed of 150r/min, adding 0.1mol of 2-aminobenzyl alcohol, performing reflux reaction for 2h, and continuing introducing the triphosgene until the molar ratio of the triphosgene to the 2-aminobenzyl alcohol reaches 6: 1, after the reaction is finished, introducing nitrogen to remove triphosgene and hydrogen chloride gas at the temperature of 80 ℃ to prepare an intermediate 1;
step A2, adding 0.5mol of intermediate 1, 200g of chlorobenzene and 10g of ethanol solution of sodium methoxide into a three-neck flask, heating to 180 ℃ in an oil bath, stirring for reaction for 7.5 hours, cooling after the reaction is finished, filtering, distilling the filtrate to remove the chlorobenzene to obtain the carbodiimide modifier, wherein the ethanol solution of the sodium methoxide is prepared from the following components in percentage by mass by taking the ratio of sodium methoxide to absolute ethyl alcohol of 3: 10, mixing;
step A3, adding 2.5g of nano silicon dioxide, 30mL of anhydrous ethanol and 30mL of deionized water into a three-neck flask, performing ultrasonic dispersion for 20min at the frequency of 40kHz, then adding 3.5mL of LKH-560, stirring and reacting for 2h at room temperature and at the rotating speed of 100r/min, after the reaction is finished, centrifuging for 10min at the rotating speed of 1000r/min, washing the precipitate for 3 times with deionized water, and drying in an oven at 60 ℃ to constant weight to obtain epoxidized silicon dioxide;
and A4, adding 5.6g of epoxidized silica, 1.7g of carbodiimide modifier and 80mL of dimethyl sulfoxide into a three-necked flask under the protection of nitrogen, controlling the temperature to be 50 ℃, stirring for reaction for 10min, then adding 1.3g of potassium hydroxide, carrying out reflux reaction for 3h, filtering after the reaction is finished, washing a filter cake with deionized water, and drying at 80 ℃ to constant weight to obtain the modified silica.
Example 2
This example provides a modified silica made by the steps of:
step A1, adding 110mL of chlorobenzene into a reaction kettle, introducing triphosgene, stirring for 25min at the rotation speed of 180r/min, adding 0.1mol of 2-aminobenzyl alcohol, performing reflux reaction for 3h, and continuing introducing the triphosgene until the molar ratio of the triphosgene to the 2-aminobenzyl alcohol reaches 6: 1, after the reaction is finished, introducing nitrogen to remove triphosgene and hydrogen chloride gas at the temperature of 82 ℃ to prepare an intermediate 1;
step A2, adding 0.5mol of intermediate 1, 200g of chlorobenzene and 10g of ethanol solution of sodium methoxide into a three-neck flask, heating to 185 ℃ in oil bath, stirring for reaction for 7.8h, cooling after the reaction is finished, filtering, distilling the filtrate to remove the chlorobenzene to obtain the carbodiimide modifier, wherein the ethanol solution of the sodium methoxide is prepared from the following components in percentage by mass of the sodium methoxide and absolute ethyl alcohol: 10, mixing;
step A3, adding 2.8g of nano silicon dioxide, 30mL of anhydrous ethanol and 30mL of deionized water into a three-neck flask, performing ultrasonic dispersion for 30min at the frequency of 45kHz, then adding 3.8mL of KH-560, stirring and reacting for 3h at room temperature and the rotation speed of 150r/min, after the reaction is finished, centrifuging for 12min at the rotation speed of 1200r/min, washing the precipitate with deionized water for 4 times, and drying in an oven at the temperature of 60 ℃ to constant weight to obtain epoxidized silicon dioxide;
step A4, under the protection of nitrogen, adding 5.8g of epoxidized silica, 1.9g of carbodiimide modifier and 85mL of dimethyl sulfoxide into a three-neck flask, controlling the temperature to be 58 ℃, stirring for reaction for 10min, then adding 1.4g of potassium hydroxide, carrying out reflux reaction for 4h, filtering after the reaction is finished, washing a filter cake with deionized water, and drying at 80 ℃ to constant weight to obtain the modified silica.
Example 3
This example provides a modified silica made by the steps of:
step A1, adding 120mL of chlorobenzene into a reaction kettle, introducing triphosgene, stirring for 30min at the rotation speed of 200r/min, adding 0.1mol of 2-aminobenzyl alcohol, performing reflux reaction for 4h, and continuing introducing the triphosgene until the molar ratio of the triphosgene to the 2-aminobenzyl alcohol reaches 6: 1, after the reaction is finished, introducing nitrogen to remove triphosgene and hydrogen chloride gas at the temperature of 85 ℃ to prepare an intermediate 1;
step A2, adding 0.5mol of intermediate 1, 200g of chlorobenzene and 10g of ethanol solution of sodium methoxide into a three-neck flask, heating to 190 ℃ in an oil bath, stirring for reaction for 8.5 hours, cooling after the reaction is finished, filtering, distilling the filtrate to remove the chlorobenzene to obtain the carbodiimide modifier, wherein the ethanol solution of the sodium methoxide is prepared from the following components in percentage by mass of the sodium methoxide and absolute ethyl alcohol: 10, mixing the components;
step A3, adding 3.2g of nano silicon dioxide, 30mL of anhydrous ethanol and 30mL of deionized water into a three-neck flask, performing ultrasonic dispersion for 40min at the frequency of 50kHz, then adding 4.2mL of KH-560, stirring and reacting for 4h at room temperature and at the rotation speed of 200r/min, after the reaction is finished, centrifuging for 15min at the rotation speed of 1500r/min, washing precipitates with deionized water for 5 times, and drying in an oven at 60 ℃ to constant weight to obtain epoxidized silicon dioxide;
step A4, under the protection of nitrogen, adding 7.2g of epoxidized silica, 2.4g of carbodiimide modifier and 90mL of dimethyl sulfoxide into a three-neck flask, controlling the temperature to be 60 ℃, stirring for reaction for 10min, then adding 1.5g of potassium hydroxide, carrying out reflux reaction for 5h, filtering after the reaction is finished, washing a filter cake with deionized water, and drying at 80 ℃ to constant weight to obtain the modified silica.
Example 4
The embodiment provides an auxiliary agent, which is prepared by the following steps:
step B1, adding 7g of p-nitrobenzoic acid into a three-neck flask, slowly dripping 110mL of sodium hydroxide solution with the mass fraction of 12% into the three-neck flask, dripping 100mL of glucose aqueous solution with the mass fraction of 60% into the three-neck flask under 70 ℃ oil bath, cooling to 20 ℃ after dripping is finished, stirring for reaction for 24 hours, dripping acetic acid to adjust the pH value to 6 after the reaction is finished, precipitating, filtering, washing a filter cake with deionized water for 3 times, and drying at 60 ℃ for 12 hours to obtain an azo compound;
and step B2, adding 0.1mol of azo compound, 0.1mol of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, p-toluenesulfonic acid, 0.05mol of bis (2-hydroxyethyl) disulfide and 100mL of toluene into a three-neck flask, heating to reflux, stirring, reacting for 4 hours, cooling to room temperature after the reaction is finished, adding a 0.1mol/L sodium bicarbonate solution to adjust the pH to 7, separating, drying an organic layer with anhydrous calcium chloride, and distilling under reduced pressure to obtain an auxiliary agent, wherein the dosage of the p-toluenesulfonic acid is 3% of the total mass of the azo compound, the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and the bis (2-hydroxyethyl) disulfide.
Example 5
This example provides an additive, which is prepared by the following steps:
step B1, adding 7g of p-nitrobenzoic acid into a three-neck flask, slowly dripping 115mL of sodium hydroxide solution with the mass fraction of 12% into the three-neck flask, dripping 100mL of glucose aqueous solution with the mass fraction of 60% into the three-neck flask under 70 ℃ oil bath, cooling to 20 ℃ after dripping is finished, stirring for reaction for 24 hours, dripping acetic acid to adjust the pH value to 6 after the reaction is finished, precipitating, filtering, washing a filter cake with deionized water for 4 times, and drying at 60 ℃ for 12 hours to obtain an azo compound;
and step B2, adding 0.1mol of azo compound, 0.1mol of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, p-toluenesulfonic acid, 0.05mol of bis (2-hydroxyethyl) disulfide and 110mL of toluene into a three-neck flask, heating to reflux, stirring, reacting for 5 hours, cooling to room temperature after the reaction is finished, adding a 0.1mol/L sodium bicarbonate solution to adjust the pH to 7, separating, drying an organic layer with anhydrous calcium chloride, and distilling under reduced pressure to obtain an auxiliary agent, wherein the dosage of the p-toluenesulfonic acid is 4% of the total mass of the azo compound, the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and the bis (2-hydroxyethyl) disulfide.
Example 6
This example provides an additive, which is prepared by the following steps:
step B1, adding 7g of p-nitrobenzoic acid into a three-neck flask, slowly dripping 120mL of sodium hydroxide solution with the mass fraction of 12% into the three-neck flask, dripping 100mL of glucose aqueous solution with the mass fraction of 60% into the three-neck flask under an oil bath at 70 ℃, cooling to 20 ℃ after dripping is finished, stirring for reaction for 24 hours, dripping acetic acid to adjust the pH value to 6 after the reaction is finished, precipitating, filtering, washing a filter cake with deionized water for 5 times, and drying at 60 ℃ for 12 hours to obtain an azo compound;
and step B2, adding 0.1mol of azo compound, 0.1mol of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, p-toluenesulfonic acid, 0.05mol of bis (2-hydroxyethyl) disulfide and 120mL of toluene into a three-neck flask, heating to reflux, stirring, reacting for 6h, cooling to room temperature after the reaction is finished, adding a 0.1mol/L sodium bicarbonate solution to adjust the pH to 8, separating, drying an organic layer with anhydrous calcium chloride, and distilling under reduced pressure to obtain an auxiliary agent, wherein the dosage of the p-toluenesulfonic acid is 5% of the total mass of the azo compound, the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and the bis (2-hydroxyethyl) disulfide.
Example 7
The shape memory thermoplastic elastomer material comprises the following raw materials in parts by weight: 4 parts of styrene-ethylene-butylene-styrene block copolymer (SEBS), 20 parts of styrene-butadiene-styrene block copolymer (SBS), 25 parts of plasticizer, 30 parts of polylactic acid, 1 part of modified silicon dioxide of example 1, 5 parts of compatilizer and 1 part of auxiliary agent of example 4;
the shape memory thermoplastic elastomer material is prepared by the following steps:
step one, adding a plasticizer, SEBS and SBS into a high-speed mixer, uniformly mixing, heating to 50 ℃, adding polylactic acid, modified silicon dioxide, a compatilizer and an auxiliary agent, keeping the temperature, stirring and mixing for 30min to obtain a mixture;
and secondly, transferring the mixture into a double-screw extruder, performing melt extrusion and granulation to obtain the shape memory thermoplastic elastomer material, wherein the rotating speed of a screw is 25r/min, the feeding amount is 10kg/h, and the temperature of a machine barrel is set to be 180 ℃/190 ℃/200 ℃/190 ℃.
Wherein, the plasticizer is soybean oil, and the compatilizer is glycidyl methacrylate grafted ethylene-butadiene block copolymer (SBS-g-GMA).
Example 8
The shape memory thermoplastic elastomer material comprises the following raw materials in parts by weight: 5 parts of styrene-ethylene-butylene-styrene block copolymer (SEBS), 22 parts of styrene-butadiene-styrene block copolymer (SBS), 28 parts of plasticizer, 35 parts of polylactic acid, 2 parts of modified silicon dioxide of example 1, 6 parts of compatilizer and 1.5 parts of auxiliary agent of example 4;
the shape memory thermoplastic elastomer material is prepared by the following steps:
step one, adding a plasticizer, SEBS and SBS into a high-speed mixer, uniformly mixing, heating to 50 ℃, adding polylactic acid, modified silicon dioxide, a compatilizer and an auxiliary agent, keeping the temperature, stirring and mixing for 30min to obtain a mixture;
and secondly, transferring the mixture into a double-screw extruder, performing melt extrusion and granulation to obtain the shape memory thermoplastic elastomer material, wherein the rotating speed of a screw is 25r/min, the feeding amount is 10kg/h, and the temperature of a machine barrel is set to be 180 ℃/190 ℃/200 ℃/190 ℃.
Wherein, the plasticizer is soybean oil, and the compatilizer is glycidyl methacrylate grafted ethylene-butadiene block copolymer (SBS-g-GMA).
Example 9
The shape memory thermoplastic elastomer material comprises the following raw materials in parts by weight: 7 parts of styrene-ethylene-butylene-styrene block copolymer (SEBS), 25 parts of styrene-butadiene-styrene block copolymer (SBS), 32 parts of plasticizer, 40 parts of polylactic acid, 3 parts of modified silicon dioxide of example 1, 7 parts of compatilizer and 2 parts of auxiliary agent of example 4;
the shape memory thermoplastic elastomer material is prepared by the following steps:
step one, adding a plasticizer, SEBS and SBS into a high-speed mixer, uniformly mixing, heating to 50 ℃, adding polylactic acid, modified silicon dioxide, a compatilizer and an auxiliary agent, keeping the temperature, stirring and mixing for 30min to obtain a mixture;
and secondly, transferring the mixture into a double-screw extruder, performing melt extrusion and granulation to obtain the shape memory thermoplastic elastomer material, wherein the rotating speed of a screw is 25r/min, the feeding amount is 10kg/h, and the temperature of a machine barrel is set to be 180 ℃/190 ℃/200 ℃/190 ℃.
Wherein, the plasticizer is soybean oil, and the compatilizer is glycidyl methacrylate grafted ethylene-butadiene block copolymer (SBS-g-GMA).
Comparative example 1
The modified silica in example 7 was replaced with nano silica sold by new chemical materials of zhengzhou west deli ltd, and the rest of raw materials and preparation process were not changed.
Comparative example 2
The auxiliary agent in example 8 was removed, and the rest of the raw materials and the preparation process were unchanged.
Comparative example 3
This comparative example is the product of example 1 of the invention patent publication No. CN 105838049A.
The shape memory elastomer materials of examples 7 to 9 and comparative examples 1 to 3 were put into a flat vulcanizing agent, and pressure-maintained at 180 ℃ and 15MPa for 2min, molded into a 1mm flat plate, followed by cutting out a rectangular bar (40 mm. times.10 mm. times.1 mm), and then subjected to a performance test:
and (3) testing tensile property: testing according to ASTM D638, wherein the tensile speed is 20 mm/min;
testing the shape memory performance: drawing a gauge length on the prepared dumbbell-shaped sample strip, and setting the gauge length as S0Placing the sample strip in a hot water bath, keeping the temperature for 5min, and applying an external force to stretch the sample strip along the gauge length direction by a distance S1Rapidly cooled at room temperature while maintaining an external force, and removed when the deformation is fixedForce, measuring the distance between two marked lines as S2Then the shape fixation ratio R can be obtainedf(Shape fixing ratio)：Rf＝(S1-S2)/(S1-S0)×100％
Placing the sample strip with fixed deformation in a hot water bath, recovering the shape of the sample strip, and measuring the distance between the two marked lines to be S3Then the shape recovery rate R can be obtainedr(Shape recovery ratio)：Rr＝(S3-S0)/(S2-S0)×100％；
Hydrolysis resistance: placing the prepared sample strips in an epoxy aging oven to perform a constant temperature and humidity aging test under the condition of 70 ℃/80% RH, and testing the elongation at break after 72 h;
self-repairing performance: cutting a 5 mm-deep cross wound on the surface of each group of sample strips by using a blade, and heating at 40 ℃ for 2h to determine whether the wound is healed;
the test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the shape memory elastomer materials obtained in examples 7 to 9 have good mechanical properties, shape memory properties, hydrolysis resistance and oxidation resistance, and good self-healing properties.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (1)
1. The shape memory thermoplastic elastomer material is characterized by comprising the following raw materials in parts by weight: 4-7 parts of styrene-ethylene-butylene-styrene block copolymer, 20-25 parts of styrene-butadiene-styrene block copolymer, 25-32 parts of plasticizer, 30-40 parts of polylactic acid, 1-3 parts of modified silicon dioxide, 5-7 parts of compatilizer and 1-2 parts of auxiliary agent;
wherein, the modified silicon dioxide is prepared by the following steps:
step A1, adding chlorobenzene into a reaction kettle, introducing triphosgene, stirring, adding 2-aminobenzyl alcohol, refluxing for 2-4h, and continuously introducing triphosgene until the molar ratio of triphosgene to 2-aminobenzyl alcohol reaches 6: 1, after the reaction is finished, introducing nitrogen at the temperature of 80-85 ℃ to remove triphosgene and hydrogen chloride gas, and preparing an intermediate 1;
step A2, mixing the intermediate 1, chlorobenzene and an ethanol solution of sodium methoxide, refluxing, stirring, reacting for 7.5-8.5h, filtering, and distilling to obtain a carbodiimide modifier;
step A3, performing ultrasonic dispersion on nano silicon dioxide, absolute ethyl alcohol and deionized water, adding KH-560, stirring for reaction for 2-4h, centrifuging for 10-15min, washing precipitate, and drying to obtain epoxidized silicon dioxide;
step A4, under the protection of nitrogen, mixing the epoxidized silica, the carbodiimide modifier and dimethyl sulfoxide, stirring for 10min at the temperature of 50-60 ℃, adding potassium hydroxide, carrying out reflux reaction for 3-5h, filtering after the reaction is finished, washing a filter cake with deionized water, and drying at the temperature of 80 ℃ to obtain modified silica;
the dosage ratio of chlorobenzene to 2-aminobenzyl alcohol in A1 is 100-120 mL: 0.1 mol; the dosage ratio of the intermediate 1, chlorobenzene and sodium methoxide ethanol solution in A2 is 0.5 mol: 200 g: 10g of sodium methoxide ethanol solution, wherein the mass ratio of sodium methoxide to absolute ethyl alcohol is 3: 10, mixing; the dosage ratio of the nano silicon dioxide, the absolute ethyl alcohol, the deionized water and the KH-560 in A3 is 2.5-3.2 g: 30mL of: 30mL of: 3.5-4.2 mL; the dosage ratio of the epoxy silica, the carbodiimide modifier, the dimethyl sulfoxide and the potassium hydroxide in A4 is 5.6-7.2 g: 1.7-2.4 g: 80-90 mL: 1.3-1.5 g;
the auxiliary agent is prepared by the following steps:
step B1, dropwise adding a sodium hydroxide solution into the p-nitrobenzoic acid, dropwise adding a glucose aqueous solution under an oil bath at 70 ℃, cooling to 20 ℃ after the dropwise adding is finished, stirring for reacting for 24 hours, adjusting the pH value to 6 by using acetic acid, performing suction filtration, washing a filter cake, and drying to obtain an azo compound;
step B2, mixing an azo compound, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, p-toluenesulfonic acid, bis (2-hydroxyethyl) disulfide and toluene, refluxing, stirring and reacting for 4-6h, cooling to room temperature after the reaction is finished, adding a sodium bicarbonate solution to adjust the pH to 7-8, separating liquid, drying an organic layer, and distilling under reduced pressure to obtain an auxiliary agent;
the dosage ratio of the p-nitrobenzoic acid, the sodium hydroxide solution and the glucose aqueous solution in the step B1 is 7 g: 110-120 mL: 100 mL; in step B2, the ratio of the amounts of the azo compound, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, bis (2-hydroxyethyl) disulfide and toluene was 0.1 mol: 0.1 mol: 0.05 mol: 100mL and 120mL, wherein the dosage of the p-toluenesulfonic acid is 3-5 percent of the total mass of the azo compound, the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and the bis (2-hydroxyethyl) disulfide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111334460.4A CN113999507B (en) | 2021-11-11 | 2021-11-11 | Shape memory thermoplastic elastomer material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111334460.4A CN113999507B (en) | 2021-11-11 | 2021-11-11 | Shape memory thermoplastic elastomer material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113999507A CN113999507A (en) | 2022-02-01 |
| CN113999507B true CN113999507B (en) | 2022-06-24 |
Family
ID=79928603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111334460.4A Active CN113999507B (en) | 2021-11-11 | 2021-11-11 | Shape memory thermoplastic elastomer material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113999507B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114805928B (en) * | 2022-03-10 | 2023-10-03 | 江苏森禾化工科技有限公司 | Biological base plasticizer for metaphenylene |
| CN115260725B (en) * | 2022-09-28 | 2022-12-30 | 河北尚华塑料科技有限公司 | Environment-friendly thermoplastic elastomer material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6022550A (en) * | 1996-09-18 | 2000-02-08 | Daicel Chemical Industries, Ltd. | Crosslinkable polymer composition, molded article therefrom, process for the preparation thereof, crosslinked nonwoven cloth, and process for the preparation thereof |
| CN101260220A (en) * | 2008-04-10 | 2008-09-10 | 复旦大学 | Blending polymer shape memory material and preparation method thereof |
| CN104559096A (en) * | 2014-12-16 | 2015-04-29 | 华南理工大学 | Body-heat-excited polylactic-acid-base biodegradable shape memory material, and preparation method and application thereof |
| CN105838049A (en) * | 2015-01-15 | 2016-08-10 | 上海交通大学 | Biodegradable polylactic acid based shape memory composite material and preparation method thereof |
| CN108192321A (en) * | 2017-12-01 | 2018-06-22 | 南京天朗制药有限公司 | The moulding thermoplastic elastic shape-memory material of body temperature/at room temperature |
| CN113736191A (en) * | 2021-09-06 | 2021-12-03 | 中国科学院长春应用化学研究所 | Thermotropic shape memory composite material and preparation method thereof |
-
2021
- 2021-11-11 CN CN202111334460.4A patent/CN113999507B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6022550A (en) * | 1996-09-18 | 2000-02-08 | Daicel Chemical Industries, Ltd. | Crosslinkable polymer composition, molded article therefrom, process for the preparation thereof, crosslinked nonwoven cloth, and process for the preparation thereof |
| CN101260220A (en) * | 2008-04-10 | 2008-09-10 | 复旦大学 | Blending polymer shape memory material and preparation method thereof |
| CN104559096A (en) * | 2014-12-16 | 2015-04-29 | 华南理工大学 | Body-heat-excited polylactic-acid-base biodegradable shape memory material, and preparation method and application thereof |
| CN105838049A (en) * | 2015-01-15 | 2016-08-10 | 上海交通大学 | Biodegradable polylactic acid based shape memory composite material and preparation method thereof |
| CN108192321A (en) * | 2017-12-01 | 2018-06-22 | 南京天朗制药有限公司 | The moulding thermoplastic elastic shape-memory material of body temperature/at room temperature |
| CN113736191A (en) * | 2021-09-06 | 2021-12-03 | 中国科学院长春应用化学研究所 | Thermotropic shape memory composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113999507A (en) | 2022-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113999507B (en) | Shape memory thermoplastic elastomer material | |
| HU177199B (en) | Process for producing thermoplastice polytetramethylenether-polyurethan-urea elastomeres | |
| CN112063154B (en) | Microporous repairable TPU (thermoplastic polyurethane) film material and preparation method thereof | |
| WO2006102842A1 (en) | Antibacterial shape memory polyurethane plate for orthopedics, fixing and rehabilitation, and preparation method thereof. | |
| AU2020348320A1 (en) | Developable composite biological mesh containing barium sulfate and preparation method therefor | |
| CN101050277A (en) | Copolymer of polyarylether nitrile containing chian element of iso-benzene and preparation method | |
| CN113773479B (en) | High-impact-strength liquid crystal polyarylate and preparation method and application thereof | |
| CN114573962A (en) | Degradable food packaging material | |
| CN108103610B (en) | Method for preparing polyglycolic acid fiber | |
| CN113736162A (en) | High-degradation modified plastic particle | |
| CN113817145B (en) | Polyester type biodegradable shape memory copolymer based on poly epsilon-caprolactone and preparation method thereof | |
| CN113195197A (en) | Oriented biodegradable polyurethanes | |
| CN102071491B (en) | Medicinal gullet scaffold fiber and preparation method thereof | |
| CN113527649B (en) | High-fluidity antibacterial PBAT polymer and preparation method thereof | |
| CN106700040A (en) | Method for preparing polylactic acid through twin screw reactive extrusion method and ring open polymerization method | |
| CN108641316A (en) | A kind of polymer composite, preparation and application | |
| CN111393817B (en) | Completely-stereo high-toughness polylactic acid stereo compound and preparation method thereof | |
| CN112625412A (en) | Preparation method of poly (4-hydroxybutyrate) low-temperature thermoplastic medical splint | |
| CN116478414B (en) | Phase change material and preparation method and application thereof | |
| CN1238400C (en) | Method for chain extending poly paradioxygen cyclohexanone | |
| CN110343350B (en) | Preparation method of PVA composite material with shape memory function | |
| CN111269426B (en) | Preparation method of polylactic acid-polybutyrolactam bio-based degradable copolymer | |
| CN103059203A (en) | Preparation method of acetoacetyl modified ethylene-vinyl alcohol copolymer | |
| CN114015214B (en) | Polylactic acid/degradable polyester elastomer blend and preparation method thereof | |
| CN117820788A (en) | Production process of high-toughness corrosion-resistant PVC material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |