CN115368720A - Degradable polymer nano composite material and preparation method thereof - Google Patents
Degradable polymer nano composite material and preparation method thereof Download PDFInfo
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- CN115368720A CN115368720A CN202211220072.8A CN202211220072A CN115368720A CN 115368720 A CN115368720 A CN 115368720A CN 202211220072 A CN202211220072 A CN 202211220072A CN 115368720 A CN115368720 A CN 115368720A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- 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
Abstract
The invention discloses a degradable polymer nano composite material and a preparation method thereof. The degradable polymer nano composite material comprises the following raw materials in percentage by mass: degradable polymer: 77 to 99.4 percent, and inorganic nano material: 0.1 to 15 percent, chain extender: 0.5 to 8 percent. The preparation method specifically comprises the following steps: and loading the chain extender on the surface of the inorganic nano material, drying, uniformly mixing with the degradable polymer, melting and blending at a certain temperature, reacting and extruding, and molding to obtain the degradable polymer nano composite material. The invention has the beneficial effects that: the aim of improving the mechanical property and the thermodynamic property of the biodegradable polymer is finally realized through chemical crosslinking and the reinforcing and toughening effect of the nano particles, and the problems of higher production and application cost, insufficient mechanical property and poorer thermal stability in the application process of the current biodegradable material are solved; simple operation and low production and processing cost.
Description
Technical Field
The invention relates to the technical field of biodegradable materials, in particular to a degradable polymer nano composite material and a preparation method thereof.
Background
With the continuous development of socioeconomic and the rapid increase of the world population, the total yield of plastics keeps on a rapidly increasing situation. However, the plastic product is a 'double-edged sword', which provides great convenience for human life and promotes the development of related industries, and also seriously threatens the human living environment due to the problem of difficult degradation. Therefore, the development of environmentally friendly degradable plastics has become a research hotspot. The traditional process route is that some biological inducers (such as plasticized starch and the like) and photosensitizers are added into the plastic, which can accelerate the degradation of plastic products, but can not completely degrade the plastic into water and carbon dioxide in a short time. The waste plastics still cause certain damage to the global environment when being buried and incinerated. In the service life of the completely biodegradable plastic, not only can various properties meet the use requirements, but also the completely biodegradable plastic can be degraded into substances harmless to the environment after being used. Therefore, biodegradable plastics are considered to be one of the most effective ways to solve the problem of plastic contamination.
At present, the most commonly used degradable plastics are mainly polylactic acid (PLA), polyhydroxyalkanoate (PHA), polycaprolactone (PCL), polybutylene adipate/terephthalate (PBAT), polyglycolic acid (PGA), and the like. However, biodegradable plastics generally have the disadvantages of higher production cost, insufficient strength or toughness, lower Vicat softening point and poorer thermal stability. When PLA is used for preparing tableware, the toughness of the tableware cannot be met due to the brittleness and poor toughness of the PLA. In addition, the heat resistance of PLA is not high, the Vicat softening point is low, and the heat resistance requirement of tableware cannot be met, so that the application of PLA in the aspect of degradable tableware is limited. At present, the toughness of the composite material is improved mainly by adding substances such as fiber, wood, calcium carbonate and the like with good toughness and low price for blending modification; the heat resistance of PLA is improved by trapping free radicals, improving the crystallinity of PLA, improving the crystallization efficiency and the like. However, scientists have not studied and applied inorganic nano materials such as nano silicon aluminum and the like in the aspect of degradable plastics.
Disclosure of Invention
The invention provides a degradable polymer nano composite material for improving mechanical property and thermal stability and a preparation method thereof, aiming at overcoming the defects of higher production and application cost, insufficient mechanical property and poor thermal stability in the application process of a biodegradable material in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a degradable polymer nanocomposite comprises the following raw materials in percentage by mass: degradable polymer: 77-99.4%, inorganic nano material: 0.1-15%, chain extender: 0.5 to 8 percent.
Wherein: the inorganic nano material has better hydrothermal stability, the surface performance of the inorganic nano material is easy to adjust, a stable chemical structure can be formed between the inorganic nano material and a molecular chain of a degradable macromolecule, and the inorganic nano material can be prepared into stable nano particles so as to play the reinforcing effect of the nano particles, and has good application prospect in the aspect of biodegradable polymers. The chain extender is loaded and modified on the inorganic nano material, and then during the process of melting and mixing, abundant reactive groups such as hydroxyl on the surface of the inorganic nano material and the terminal hydroxyl or carboxyl of a molecular chain in the biodegradable polymer are subjected to chemical reaction, so that a stable cross-linked structure is formed. Meanwhile, the nano particles have relatively few surface defects and larger surface energy, are easy to combine with other atoms and are stable, so that the nano particles can be tightly combined with a high polymer base material and have better compatibility. When external force is applied, the nano particles are not easy to separate from the matrix material, and the borne external stress can be better transmitted. Meanwhile, under the interaction of the stress field, more microcracks and plastic deformation can be generated in the material, the yield of the matrix material can be triggered, and a large amount of impact energy is consumed, so that the aim of simultaneously reinforcing and toughening is fulfilled. Meanwhile, the thermal stability of the inorganic nano material and the nucleating agent function of the inorganic nano particles in the degradable polymer nano composite material are utilized, so that the crystallization rate and the crystallinity of the polymer are improved, and the purpose of improving the thermal stability of the degradable nano composite material is further achieved. In conclusion, the aim of improving the mechanical property and the thermodynamic property of the biodegradable polymer is finally realized through the chemical crosslinking and the reinforcing and toughening effect of the nano particles, and the problems of high production and application cost, insufficient mechanical property and poor thermal stability in the application process of the current biodegradable material are solved.
Preferably, the inorganic nano material has the morphological characteristics of nano sheet shape or nano needle shape.
Preferably, the inorganic nano material is one or more of an inorganic nano silicon-aluminum material, inorganic nano montmorillonite, inorganic nano graphene oxide and a graphitized nano carbon sheet.
Preferably, the chain extender is one selected from glycerol, 1, 4-butanediol, 1, 6-hexanediol and Extenders polymer type chain Extenders.
Preferably, the chain extender is dissolved in a solvent, then is loaded on the inorganic nano material in a volume impregnation mode, and finally is volatilized and dried.
Preferably, the solvent is one of acetone, ethanol, cyclohexane, petroleum ether and n-hexane.
Preferably, the degradable polymer is selected from one or more of polylactic acid, polybutylene terephthalate-adipate, polyhydroxybutyrate, polyhydroxyalkanoate, polybutylene succinate, polycaprolactone and polylactic acid/glycolic acid.
The invention also provides a preparation method of the degradable polymer nano composite material, which comprises the following steps: and loading the chain extender on the surface of the inorganic nano material, drying, uniformly mixing with the degradable polymer, melting and blending at a certain temperature, reacting and extruding, and molding to obtain the degradable polymer nano composite material.
The degradable polymer nano composite material prepared by the invention maintains good biodegradability, improves the mechanical strength and the heat resistance of the degradable polymer, and is widely suitable for manufacturing degradable products such as daily necessities, degradable tableware, degradable plastic industrial appliances, degradable films and the like. The invention has the advantages of wide raw material source, simple processing technology, lower production cost, easy production and practical application value.
Preferably, the inorganic nano material modified by the chain extender and the degradable polymer are uniformly mixed, then are added into an internal mixer for melt blending, and the melt after mixing is added into a double-screw extruder for reaction and extrusion.
Preferably, the reaction temperature of each zone of the internal mixer is 100-200 ℃, the rotating speed of the internal mixer is 30-250 r/min, and the mixing time of the internal mixer is 3-20 min; the temperature range of each section of the double-screw extruder is 100-240 ℃, and the rotating speed of the double-screw extruder is 50-300 r/min; the molding is one of injection molding or hot press molding.
The invention has the beneficial effects that: (1) Compared with the traditional modifiers such as filler and the like, the inorganic nano material has the advantages of adjustable surface property, adjustable nano particle appearance, adjustable nano particle size and the like, has the characteristics of no toxicity, greenness and environmental protection, and can be designed differently according to the requirements of different materials and use environments so as to meet the requirements in various aspects; (2) The preparation method of the degradable polymer nanocomposite provided by the invention is simple to operate and low in production and processing cost; (3) The mechanical property and Vicat softening point of the degradable polymer nanocomposite prepared by the method provided by the invention are obviously improved compared with the traditional biodegradable polymer.
Detailed Description
The invention is further described with reference to specific embodiments.
A degradable polymer nanocomposite comprises the following raw materials in percentage by mass: degradable polymer: 77-99.4%, inorganic nano material: 0.1-15%, chain extender: 0.5 to 8 percent. The inorganic nano material has the shape characteristics of nano sheet or nano needle. The inorganic nano material is one or more of inorganic nano silicon-aluminum material, inorganic nano montmorillonite, inorganic nano graphene oxide and graphitized nano carbon sheet. The chain extender is one selected from glycerol, 1, 4-butanediol, 1, 6-hexanediol and Extenders polymer chain Extenders. The chain extender is firstly dissolved in a solvent, then loaded on the inorganic nano material by adopting a vacuum equal-volume impregnation mode, and finally volatilized and dried. The solvent is one of acetone, ethanol, cyclohexane, petroleum ether and n-hexane. The degradable polymer is selected from one or more of polylactic acid (PLA), polybutylene terephthalate adipate (PBAT), polyhydroxybutyrate (PHB), polyhydroxyalkanoate (PHA), polybutylene succinate (PBS), polycaprolactone (PCL) and polylactic acid/glycolic acid (PLGA). The preparation method of the degradable polymer nanocomposite specifically comprises the following steps: and loading the chain extender on the surface of the inorganic nano material, drying, uniformly mixing with the degradable polymer, melting and blending at a certain temperature, reacting and extruding, and molding to obtain the degradable polymer nano composite material. The chain extender loaded and modified inorganic nano material and the degradable polymer are uniformly mixed, then are added into an internal mixer for melt blending, and the melt after mixing is added into a double-screw extruder for reaction and extrusion. The reaction temperature of each area of the internal mixer is 100-200 ℃, the rotating speed of the internal mixer is 30-250 r/min, and the mixing time of the internal mixer is 3-20 min; the temperature range of each section of the double-screw extruder is 100-240 ℃, and the rotating speed of the double-screw extruder is 50-300 r/min; the molding is one of injection molding or hot press molding.
Example 1:
taking 8 parts of the mixture with a specific surface area of 420m 2 Putting the nano flaky montmorillonite in vacuum equipment, removing adsorbed air, water and the like by vacuum desorption, dissolving 1.0 part of Joncryl ADR chain extender in a proper amount of acetone, then soaking the chain extender on the montmorillonite, volatilizing, drying and the like, putting the chain extender, 71 parts of polylactic acid and 20 parts of PBAT together into a high-speed mixer for mixing, adding the mixture into a Hakke internal mixer, carrying out melt blending at 180 ℃ at the rotating speed of 40r/min for mixing for 10min, then carrying out melt extrusion on the melt through a double-screw extruder at the rotating speed of 50r/min, controlling the temperature of each section at 185-195 ℃, preparing a sample of the degradable polymer nano composite material through an injection molding machine after extrusion, and then testing the tensile property and the Vicat softening point.
Example 2:
taking 10 parts of the mixture with the specific surface area of 420m 2 Putting the nano flaky SAPO-34 molecular sieve in vacuum equipment, removing adsorbed air, water and the like by vacuum desorption, dissolving 2.0 parts of 1, 4-butanediol in a proper amount of cyclohexane, dipping the mixture on the SAPO-34 molecular sieve, volatilizing, drying and the like, putting the mixture and 88 parts of polylactic acid into a high-speed mixer together for mixing, adding the mixture into a Hakke internal mixer, carrying out melt blending at 180 ℃ at the rotating speed of 40r/min for mixing for 10min, carrying out melt extrusion on the melt through a double-screw extruder at the rotating speed of 50r/min, controlling the temperature of each section at 185-195 ℃, preparing a sample of the degradable polymer nano composite material through an injection molding machine after extrusion, and testing the tensile property and the Vicat softening point.
Example 3:
putting 5 parts of inorganic nano graphene oxide into vacuum equipment, removing adsorbed air and moisture by vacuum desorption, dissolving 0.75 part of Joncryl ADR chain extender in a proper amount of petroleum ether, soaking the inorganic nano graphene oxide chain extender on the inorganic nano graphene oxide, volatilizing, drying and the like, putting 80 parts of polylactic acid and 14.25 parts of polycaprolactone into a high-speed mixer together, mixing the mixture with a Hakke internal mixer, carrying out melt blending at 170 ℃, wherein the rotating speed is 40r/min, mixing for 6min, carrying out melt extrusion by a double-screw extruder, controlling the rotating speed at 50r/min, controlling the temperature of each section at 170-180 ℃, preparing a sample of the polymer nano composite material by an injection molding machine after extrusion, and testing the tensile property and the Vicat softening point of the sample.
Example 4:
taking 4 parts of the mixture with the specific surface area of 420m 2 Per g of nano sheet MCM-22 molecular sieve and 3 parts of specific surface area of 408m 2 Putting a/g nanometer needle-shaped ZSM-5 molecular sieve into a ball mill, uniformly mixing, putting into vacuum equipment, removing adsorbed air, water and the like through vacuum desorption, dissolving 0.75 part of Joncryl ADR chain extender and 3 parts of glycerol in a proper amount of ethanol, soaking on a mixed inorganic nanometer material, volatilizing, drying and the like, putting 89.25 parts of polybutylene terephthalate-adipate into a high-speed mixer together, adding into a Hakke internal mixer, performing melt blending at 180 ℃ for 10min at the rotating speed of 40r/min, mixing, performing melt extrusion through a double-screw extruder at the rotating speed of 50r/min, controlling the temperature of each section at 185-195 ℃, preparing a sample of the degradable polymer nanometer composite material through an injection molding machine after extrusion, and testing the tensile property and the Vicat softening point.
Example 5:
taking 10 parts of the mixture with a specific surface area of 431m 2 Putting the nano flaky MCM-56 molecular sieve in vacuum equipment, removing adsorbed air, water and the like through vacuum desorption, dissolving 2 parts of 1, 4-butanediol in a proper amount of cyclohexane, soaking the solution on the MCM-56 molecular sieve, volatilizing, drying and the like, putting the solution and 88 parts of polylactic acid into a high-speed mixer together for mixing, adding the mixture into a Hakke internal mixer for melt blending at the temperature of 181 ℃, mixing for 12min at the rotating speed of 45r/min, then melt extruding the melt through a double-screw extruder at the rotating speed of 60r/min, controlling the temperature of each section at 186-192 ℃, preparing a sample of the degradable polymer nanocomposite through an injection molding machine after extrusion, and testing the tensile property and the Vicat softening point of the sample。
Comparative example 1:
adding 100 parts of polylactic acid into a Hakke internal mixer, melting and blending at 180 ℃ for 10min at the rotation speed of 100r/min, and then melting and extruding the melt through a double-screw extruder at the rotation speed of 50r/min, wherein the temperature of each section is controlled at 180-200 ℃.
Comparative example 2:
taking 90 parts of polylactic acid and 10 parts of polylactic acid/glycollic acid, mixing in a high-speed mixer, adding into a Hakke internal mixer, melting and blending at 180 ℃, wherein the rotation speed is 100r/min, mixing for 10min, then melting and extruding the melt through a double-screw extruder, wherein the rotation speed is 50r/min, and the temperature of each section is controlled at 180-200 ℃.
The blend polyesters prepared in comparative examples 1-2 were molded to prepare a standard sample of a degradable polylactic acid-based composite material, and mechanical properties thereof were measured.
The specific performance test table is as follows:
| sample(s) | Tensile strength/MPa | Elongation at break/% | Vicat softening point/. Degree C |
| Example 1 | 78.5 | 10.3 | 161 |
| Example 2 | 72.7 | 9.1 | 154 |
| Example 3 | 63.0 | 35.2 | 152 |
| Example 4 | 68.9 | 12.7 | 157 |
| Example 5 | 70.6 | 11.9 | 159 |
| Comparative example 1 | 64.2 | 5.3 | 64 |
| Comparative example 2 | 58.3 | 6.5 | 60 |
Claims (10)
1. The degradable polymer nanocomposite is characterized by comprising the following raw materials in percentage by mass: degradable polymer: 77 to 99.4 percent, and inorganic nano-materials: 0.1 to 15 percent of chain extender: 0.5 to 8 percent.
2. The degradable polymer nanocomposite of claim 1 wherein said inorganic nanomaterial has a nanosheet or nanoneedle morphology.
3. The degradable polymer nano composite material of claim 1 or 2, wherein the inorganic nano material is one or more of inorganic nano silicon-aluminum material, inorganic nano montmorillonite, inorganic nano graphene oxide and graphitized nano carbon sheet.
4. The degradable polymer nanocomposite as claimed in claim 1, wherein the chain extender is one selected from glycerin, 1, 4-butanediol, 1, 6-hexanediol, extenders polymeric chain Extenders.
5. The degradable polymer nanocomposite as claimed in claim 1 or 4, wherein the chain extender is dissolved in the solvent, loaded on the inorganic nanomaterial by volume impregnation, and finally volatilized and dried.
6. The degradable polymer nanocomposite as claimed in claim 5, wherein the solvent is one of acetone, ethanol, cyclohexane, petroleum ether, and n-hexane.
7. The degradable polymer nano composite material and the preparation method thereof as claimed in claim 1, wherein the degradable polymer is selected from one or more of polylactic acid, polybutylene terephthalate-adipate, polyhydroxybutyrate, polyhydroxyalkanoate, polybutylene succinate, polycaprolactone, polylactic acid/glycolic acid.
8. A preparation method of a degradable polymer nano composite material is characterized by comprising the following steps: and loading the chain extender on the surface of the inorganic nano material, drying, uniformly mixing with the degradable polymer, melting and blending at a certain temperature, reacting and extruding, and molding to obtain the degradable polymer nano composite material.
9. The method for preparing the degradable polymer nano composite material of claim 8, wherein the inorganic nano material modified by the chain extender and the degradable polymer are uniformly mixed, and then are added into an internal mixer for melt blending, and the melt after mixing is added into a double-screw extruder for reaction and extrusion.
10. The method for preparing the degradable polymer nanocomposite material according to claim 9, wherein the reaction temperature of each zone of the internal mixer is 100 to 200 ℃, the rotation speed of the internal mixer is 30 to 250r/min, and the mixing time of the internal mixer is 3 to 20min; the temperature range of each section of the double-screw extruder is 100 to 240 ℃, and the rotating speed of the double-screw extruder is 50 to 300r/min; the molding is one of injection molding or hot press molding.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115819935A (en) * | 2022-12-16 | 2023-03-21 | 福州大学 | High-wear-resistance high-strength degradable high polymer material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115819935A (en) * | 2022-12-16 | 2023-03-21 | 福州大学 | High-wear-resistance high-strength degradable high polymer material |
| CN115819935B (en) * | 2022-12-16 | 2024-03-29 | 福州大学 | High-wear-resistance high-strength degradable high polymer material |
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