CN111303598A - Preparation method of calcium carbonate nanorod modified polylactic acid material - Google Patents
Preparation method of calcium carbonate nanorod modified polylactic acid material Download PDFInfo
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- CN111303598A CN111303598A CN202010262429.3A CN202010262429A CN111303598A CN 111303598 A CN111303598 A CN 111303598A CN 202010262429 A CN202010262429 A CN 202010262429A CN 111303598 A CN111303598 A CN 111303598A
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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
- C08K9/00—Use of pretreated ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08K2201/00—Specific properties of additives
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- C08K2201/004—Additives being defined by their length
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Abstract
The invention relates to a preparation method of a calcium carbonate nanorod modified polylactic acid material, which comprises the following steps of 1) injecting a calcium chloride solution into a mixed solution of sodium hydroxide, sodium carbonate and sodium chloride in batches, and after the addition is finished, continuously stirring and reacting for 0.5h to obtain calcium carbonate nanorods; 2) adding sodium laurate hot ethanol solution, and carrying out reflux reaction; 3) premixing the modified calcium carbonate nano-rods and polylactic acid, and then melting and blending; 4) and carrying out hot press molding to obtain the calcium carbonate nanorod modified polylactic acid material. The method can improve the compatibility of the inorganic nano particles and the polylactic acid, so that the inorganic particles are uniformly dispersed in the polylactic acid, and the melt viscosity is reduced while the mechanical properties such as tensile strength and the like are improved.
Description
Technical Field
The invention relates to a composite material of an inorganic nano material and a polymer, in particular to a preparation method of a calcium carbonate nanorod modified polylactic acid material.
Background
Lactic acid is also called polylactide because it is a high molecular polyester obtained by ring-opening polymerization of lactide, which is a cyclic dimer of lactic acid. The polylactic acid has better strength, chemical inertness, easy processability, excellent biocompatibility and degradability, and is a renewable resource. The polylactic acid can be completely degraded into carbon dioxide and water after being used, thereby avoiding the problem of white pollution and being a completely degradable environment-friendly material. However, polylactic acid has disadvantages such as poor hydrophilicity, high brittleness, poor impact resistance, long degradation period, and the like, and is expensive, so that its application is restricted.
In order to improve the mechanical properties of polylactic acid, researchers try to blend inorganic materials with polylactic acid, but the interfacial bonding force of the inorganic materials and the polylactic acid is weak, so that the compatibility after the composite is extremely poor, the inorganic materials are easy to exist in the polylactic acid in a state of being agglomerated into particles, the mechanical properties of the composite cannot be improved, even the mechanical properties of the composite are reduced, and the inorganic particles are not easy to deform and flow, so that the internal friction force in the composite is greatly increased, the melt viscosity is increased, and the composite is difficult to process. How to improve the compatibility of the inorganic nanoparticles and the polylactic acid and uniformly disperse the inorganic particles in the polylactic acid, and the problem of reducing the melt viscosity while improving the mechanical properties such as tensile strength and the like of the polylactic acid still remains to be solved.
Disclosure of Invention
The invention relates to a preparation method of a calcium carbonate nanorod modified polylactic acid material, aiming at solving the technical problem of how to improve the compatibility of inorganic nanoparticles and polylactic acid, uniformly disperse the inorganic nanoparticles in the polylactic acid, improve the mechanical properties such as tensile strength and the like and reduce the melt viscosity.
A preparation method of calcium carbonate nanorod modified polylactic acid material is characterized by comprising the following steps:
1) preparing calcium carbonate nanorods: heating the mixed solution of sodium hydroxide, sodium carbonate and sodium chloride to 60-75 ℃, injecting a calcium chloride solution in batches under rapid stirring, continuously stirring and reacting for 0.5h after the addition is finished, filtering, and washing with deionized water to obtain calcium carbonate nanorods;
2) modification of calcium carbonate nanorods: adding ethanol into a reaction kettle, heating to 60-75 ℃, adding the calcium carbonate obtained in the step 1) into the reaction kettle, uniformly stirring, adding a hot ethanol solution of sodium laurate, carrying out reflux reaction for 2-3h in a water bath at 80 ℃, cooling, filtering, washing with hot ethanol, and drying;
3) preparing a composite material: premixing the modified calcium carbonate nano-rod obtained in the step 2) with polylactic acid, adding the obtained mixture into a double-roll open mill for melt blending at the temperature of 160 ℃ and 180 ℃ for 15-20min to obtain a blended product;
4) and (4) carrying out hot press molding on the blended product obtained in the step 4) to obtain the calcium carbonate nanorod modified polylactic acid material.
In the step 1), the concentration of sodium hydroxide, the concentration of sodium chloride and the concentration of sodium carbonate in the mixed solution of sodium hydroxide, sodium carbonate and sodium chloride are respectively 0.2mol/L, 0.3mol/L and 0.15 mol/L.
In the step 1), the concentration of the calcium chloride solution is 0.15mol/L, 5mL is added each time, the time interval is 5-8s, and the molar ratio of sodium carbonate to calcium chloride in the reaction process is 1: 0.7-0.9.
In step 1), the stirring speed is 10000-.
In the step 2), the mass ratio of the calcium carbonate nano-rods to the sodium laurate is about 1: 0.1-0.3.
In the step 3), the mass ratio of the modified calcium carbonate nano-rods to the polylactic acid is 0.05-0.2: 1.
Advantageous effects
According to the invention, sodium laurate is used for modifying the calcium carbonate nanorods, the polar end of the sodium laurate is adsorbed on the surface of the particles, and the fatty chain of the sodium laurate stretches outwards, so that the calcium carbonate nanorods are changed from hydrophilicity to hydrophobicity, and the compatibility of the calcium carbonate nanorods with polylactic acid is increased. The length of the nano-rod is controlled to be 600-900nm by controlling the reaction parameters in the nano-rod preparation process, so that the dispersion of calcium carbonate in polylactic acid is facilitated, and the phenomena of self winding, agglomeration and the like caused by the overlong length of the one-dimensional structure of the calcium carbonate are avoided. In a molten state, polymer molecular chains can flow relatively, the material has certain viscosity due to long separation, continuous curling and winding, and after calcium carbonate nanorods are added, the nanorods with one-dimensional structures can be oriented and arranged at a low shear rate, so that the winding among the high molecular chains is hindered, the viscosity is reduced, and the processing of the composite material is facilitated.
In the preparation process of the calcium carbonate, the concentration of sodium hydroxide and sodium carbonate is controlled, the pH value of a reaction system is controlled, the initial nucleation rate and the later anisotropic growth of the calcium carbonate are controlled by the concentration of sodium chloride and the feeding speed of calcium chloride, and the nano rod with uniform size and good dispersibility is finally obtained.
Detailed Description
The weight average molecular weight of the polymer using polylactic acid was 13.2X 104g/mol。
According to the national standard GB/T1040-2006, a WDW-2 type electronic testing machine is adopted to carry out a tensile test, the tensile strength of polylactic acid and calcium carbonate nanorod modified polylactic acid is respectively tested, the rate is 0.1cm/min, and a sample is in a strip shape of 110mm x 6mm x 4 mm.
And hot-pressing the polylactic acid modified by the polylactic acid and the calcium carbonate nano-rods into a sheet with the diameter of 3cm and the thickness of 0.2 cm. The melt rheology was measured in air at 170 ℃ using a Malvern gemi 2000 parallel plate rheometer with 1% strain, 0.1Hz frequency and 0.1cm spacing.
Example 1
1) Preparing calcium carbonate nanorods: the method comprises the following steps of (1) injecting a calcium chloride solution in batches under the conditions that the concentration of sodium hydroxide in a mixed solution of sodium hydroxide, sodium carbonate and sodium chloride is 0.2mol/L, the concentration of sodium chloride is 0.3mol/L and the concentration of sodium carbonate is 0.15mol/L, heating to 60-75 ℃, rapidly stirring, wherein the concentration of the calcium chloride solution is 0.15mol/L, 5mL is added each time, the time interval is 6s, the molar ratio of sodium carbonate to calcium chloride in the reaction process is 1: 0.9, after the addition is finished, continuously stirring for reacting for 0.5h, filtering, and washing with deionized water to obtain calcium carbonate nanorods;
2) modification of calcium carbonate nanorods: adding ethanol into a reaction kettle, heating to 70 ℃, adding the calcium carbonate obtained in the step 1) into the reaction kettle, uniformly stirring, adding a sodium laurate hot ethanol solution, wherein the mass ratio of the calcium carbonate nanorods to the sodium laurate is 1: 0.1, carrying out reflux reaction for 3 hours in a water bath at 80 ℃, cooling, filtering, washing with hot ethanol, and drying;
3) preparing a composite material: premixing the modified calcium carbonate nanorods obtained in the step 2) with polylactic acid, wherein the mass ratio of the modified calcium carbonate nanorods to the polylactic acid is 0.1: 1, adding the mixture into a double-roll open mill, and carrying out melt blending at the temperature of 160 ℃ for 15min to obtain a blended product;
4) and (3) carrying out hot press molding on the blended product obtained in the step 4) to obtain the calcium carbonate nanorod modified polylactic acid material with the tensile strength of 65MPa and the viscosity of 1.24kPa · s.
Example 2
1) Preparing calcium carbonate nanorods: the method comprises the following steps of (1) injecting a calcium chloride solution in batches under the conditions that the concentration of sodium hydroxide in a mixed solution of sodium hydroxide, sodium carbonate and sodium chloride is 0.2mol/L, the concentration of sodium chloride is 0.3mol/L and the concentration of sodium carbonate is 0.15mol/L, heating to 60-75 ℃, rapidly stirring, wherein the concentration of the calcium chloride solution is 0.15mol/L, 5mL is added each time, the time interval is 8s, the molar ratio of sodium carbonate to calcium chloride in the reaction process is 1: 0.7, continuously stirring and reacting for 0.5h after the addition is finished, filtering, and washing with deionized water to obtain calcium carbonate nanorods;
2) modification of calcium carbonate nanorods: adding ethanol into a reaction kettle, heating to 70 ℃, adding the calcium carbonate obtained in the step 1) into the reaction kettle, uniformly stirring, adding a sodium laurate hot ethanol solution, wherein the mass ratio of the calcium carbonate nanorods to the sodium laurate is 1: 0.3, carrying out reflux reaction for 3 hours in a water bath at 80 ℃, cooling, filtering, washing with hot ethanol, and drying;
3) preparing a composite material: premixing the modified calcium carbonate nanorods obtained in the step 2) with polylactic acid, wherein the mass ratio of the modified calcium carbonate nanorods to the polylactic acid is 0.2: 1, adding the obtained mixture into a double-roll open mill, and carrying out melt blending at the temperature of 160 ℃ for 15min to obtain a blended product;
4) and (3) carrying out hot press molding on the blended product obtained in the step 4) to obtain the calcium carbonate nanorod modified polylactic acid material with the tensile strength of 68MPa and the viscosity of 1.23kPa · s.
Example 3
1) Preparing calcium carbonate nanorods: the method comprises the following steps of (1) injecting a calcium nitrate solution in batches under the conditions that the concentration of sodium hydroxide in a mixed solution of sodium hydroxide, sodium carbonate and sodium nitrate is 0.2mol/L, the concentration of sodium nitrate is 0.3mol/L and the concentration of sodium carbonate is 0.15mol/L, heating to 60-75 ℃, rapidly stirring, wherein the concentration of a calcium chloride solution is 0.15mol/L, 5mL is added each time, the time interval is 6s, the molar ratio of sodium carbonate to calcium chloride in the reaction process is 1: 0.9, continuously stirring and reacting for 0.5h after the addition is finished, filtering, washing with deionized water, and obtaining calcium carbonate nanorods with non-uniform shapes and sizes;
2) modification of calcium carbonate nanorods: adding ethanol into a reaction kettle, heating to 70 ℃, adding the calcium carbonate obtained in the step 1) into the reaction kettle, uniformly stirring, adding a sodium laurate hot ethanol solution, wherein the mass ratio of the calcium carbonate nanorods to the sodium laurate is 1: 0.1, carrying out reflux reaction for 3 hours in a water bath at 80 ℃, cooling, filtering, washing with hot ethanol, and drying;
3) preparing a composite material: premixing the modified calcium carbonate nanorods obtained in the step 2) with polylactic acid, wherein the mass ratio of the modified calcium carbonate nanorods to the polylactic acid is 0.1: 1, adding the mixture into a double-roll open mill, and carrying out melt blending at the temperature of 160 ℃ for 15min to obtain a blended product;
4) and (3) carrying out hot press molding on the blended product obtained in the step 4) to obtain the calcium carbonate nanorod modified polylactic acid material with the tensile strength of 55MPa and the viscosity of 2.37kPa · s.
Example 4
1) Preparing calcium carbonate nanorods: the method comprises the following steps of (1) injecting a calcium chloride solution in batches under the conditions that the concentration of sodium hydroxide in a mixed solution of sodium hydroxide, sodium carbonate and sodium chloride is 0.2mol/L, the concentration of sodium chloride is 0.3mol/L and the concentration of sodium carbonate is 0.15mol/L, heating to 60-75 ℃, rapidly stirring, wherein the concentration of the calcium chloride solution is 0.15mol/L, 3mL is added each time, the time interval is 6s, the molar ratio of sodium carbonate to calcium chloride in the reaction process is 1: 0.9, after the addition is finished, continuously stirring and reacting for 0.5h, filtering, and washing with deionized water to obtain calcium carbonate nanospheres;
2) modification of calcium carbonate: adding ethanol into a reaction kettle, heating to 70 ℃, adding the calcium carbonate obtained in the step 1) into the reaction kettle, uniformly stirring, adding a sodium laurate hot ethanol solution, wherein the mass ratio of the calcium carbonate to the sodium laurate is 1: 0.1, carrying out reflux reaction for 3 hours in a water bath at 80 ℃, cooling, filtering, washing with hot ethanol, and drying;
3) preparing a composite material: premixing the modified calcium carbonate obtained in the step 2) with polylactic acid, wherein the mass ratio of the modified calcium carbonate nano rods to the polylactic acid is 0.1: 1, adding the mixture into a double-roll open mill, and carrying out melt blending at the temperature of 160 ℃ for 15min to obtain a blended product;
4) and (3) carrying out hot press molding on the blended product obtained in the step 4) to obtain the calcium carbonate modified polylactic acid material with the tensile strength of 46MPa and the viscosity of 2.49kPa & s.
Example 5
1) Preparing calcium carbonate nanorods: the method comprises the following steps of (1) injecting a calcium chloride solution in batches under the conditions that the concentration of sodium hydroxide in a mixed solution of sodium hydroxide, sodium carbonate and sodium chloride is 0.2mol/L, the concentration of sodium chloride is 0.3mol/L and the concentration of sodium carbonate is 0.15mol/L, heating to 60-75 ℃, rapidly stirring, wherein the concentration of the calcium chloride solution is 0.15mol/L, 5mL is added each time, the time interval is 6s, the molar ratio of sodium carbonate to calcium chloride in the reaction process is 1: 0.9, after the addition is finished, continuously stirring for reacting for 0.5h, filtering, and washing with deionized water to obtain calcium carbonate nanorods;
2) preparing a composite material: premixing the calcium carbonate nanorods obtained in the step 1) with polylactic acid, wherein the mass ratio of the calcium carbonate nanorods to the polylactic acid is 0.1: 1, adding the calcium carbonate nanorods to the polylactic acid into a double-roll open mill, and carrying out melt blending at the temperature of 160 ℃ for 15min to obtain a blended product;
4) and (3) carrying out hot press molding on the blended product obtained in the step 4) to obtain the calcium carbonate nanorod modified polylactic acid material with the tensile strength of 31MPa and the viscosity of 2.04kPa · s.
When calcium carbonate is not added, the tensile strength of the polylactic acid material is 60MPa, and the viscosity is 1.55kPa & s.
Claims (6)
1. A preparation method of calcium carbonate nanorod modified polylactic acid material is characterized by comprising the following steps:
1) preparing calcium carbonate nanorods: heating the mixed solution of sodium hydroxide, sodium carbonate and sodium chloride to 60-75 ℃, injecting a calcium chloride solution in batches under rapid stirring, continuously stirring and reacting for 0.5h after the addition is finished, filtering, and washing with deionized water to obtain calcium carbonate nanorods;
2) modification of calcium carbonate nanorods: adding ethanol into a reaction kettle, heating to 60-75 ℃, adding the calcium carbonate obtained in the step 1) into the reaction kettle, uniformly stirring, adding a hot ethanol solution of sodium laurate, carrying out reflux reaction for 2-3h at 80 ℃, cooling, filtering, washing with hot ethanol, and drying;
3) preparing a composite material: premixing the modified calcium carbonate nano-rod obtained in the step 2) with polylactic acid, adding the obtained mixture into a double-roll open mill for melt blending at the temperature of 160 ℃ and 180 ℃ for 15-20min to obtain a blended product;
4) and (4) carrying out hot press molding on the blended product obtained in the step 4) to obtain the calcium carbonate nanorod modified polylactic acid material.
2. The method of claim 1, wherein: in the step 1), the concentration of sodium hydroxide, the concentration of sodium chloride and the concentration of sodium carbonate in the mixed solution of sodium hydroxide, sodium carbonate and sodium chloride are respectively 0.2mol/L, 0.3mol/L and 0.15 mol/L.
3. The method of claim 1, wherein: in the step 1), the concentration of the calcium chloride solution is 0.15mol/L, 5mL is added each time, the time interval is 5-8s, and the molar ratio of sodium carbonate to calcium chloride in the reaction process is 1: 0.7-0.9.
4. The method of claim 1, wherein: in step 1), the stirring speed is 10000-.
5. The method of claim 1, wherein: in the step 2), the mass ratio of the calcium carbonate nano-rods to the sodium laurate is about 1: 0.1-0.3.
6. The method of claim 1, wherein: in the step 3), the mass ratio of the modified calcium carbonate nano-rods to the polylactic acid is 0.05-0.2: 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115260722A (en) * | 2022-08-15 | 2022-11-01 | 陆璐 | Preparation method of calcium carbonate nanorod modified polylactic acid material |
| CN117603567A (en) * | 2023-12-18 | 2024-02-27 | 广州洛民塑料有限公司 | Novel degradable plastic folding basket and manufacturing method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944529A (en) * | 2006-10-19 | 2007-04-11 | 上海大学 | Process for preparing biologically degradable SiO2/poly lactic acid nano composite material |
| US20130081821A1 (en) * | 2011-10-04 | 2013-04-04 | Feng Liang | Reinforcing Amorphous PLA with Solid Particles for Downhole Applications |
| CN109081955A (en) * | 2018-07-02 | 2018-12-25 | 界首市汇珠渔具有限公司 | A kind of starch-based bio degradable bionic fish bait adding modified nano calcium carbonate |
-
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- 2020-03-31 CN CN202010262429.3A patent/CN111303598B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944529A (en) * | 2006-10-19 | 2007-04-11 | 上海大学 | Process for preparing biologically degradable SiO2/poly lactic acid nano composite material |
| US20130081821A1 (en) * | 2011-10-04 | 2013-04-04 | Feng Liang | Reinforcing Amorphous PLA with Solid Particles for Downhole Applications |
| CN109081955A (en) * | 2018-07-02 | 2018-12-25 | 界首市汇珠渔具有限公司 | A kind of starch-based bio degradable bionic fish bait adding modified nano calcium carbonate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115260722A (en) * | 2022-08-15 | 2022-11-01 | 陆璐 | Preparation method of calcium carbonate nanorod modified polylactic acid material |
| CN117603567A (en) * | 2023-12-18 | 2024-02-27 | 广州洛民塑料有限公司 | Novel degradable plastic folding basket and manufacturing method thereof |
| CN117603567B (en) * | 2023-12-18 | 2024-04-05 | 广州洛民塑料有限公司 | Novel degradable plastic folding basket and manufacturing method thereof |
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