CN112480713A - Preparation method of nano calcium carbonate for filling polyethylene transparent film - Google Patents
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Abstract
The invention discloses a preparation method of nano calcium carbonate for filling a polyethylene transparent film, which comprises the steps of calcining limestone to obtain quicklime, carrying out digestion reaction on the quicklime and water to obtain Ca (OH)2, sieving, standing, and preparing into Ca (OH)2 suspension; introducing carbon dioxide mixed gas, adding the monolauryl phosphate into the suspension when the pH of the reaction suspension is less than or equal to 8, uniformly stirring, and continuously introducing carbon dioxide for reaction; when the pH value of the system is less than or equal to 7, continuously introducing the carbon dioxide mixed gas, and stably existing for 0.5-1.5h when the pH value of the system is less than or equal to 7; and adding an aluminate coupling agent solution to carry out wet surface modification on the calcium carbonate, and finally carrying out filter pressing, drying and sieving to obtain the nano calcium carbonate. The nano calcium carbonate particles prepared by the method have good dispersibility, complete particle appearance and good compatibility with polyethylene; after the polyethylene film is filled, the polyethylene film has high transparency, excellent mechanical property and good processability.
Description
Technical Field
The invention belongs to the technical field of inorganic materials, and particularly relates to a preparation method of nano calcium carbonate for filling a polyethylene transparent film.
Background
Nano calcium carbonate is the most commonly used filler for plastics, coatings, rubber, inks, sealants, paper making and the like. The unmodified nano calcium carbonate is hydrophilic and oleophobic, so that the nano calcium carbonate has poor dispersibility in a polymer composite material, and for most applications, the nano calcium carbonate needs surface modification to facilitate oleophylic and hydrophobic properties and improve dispersibility. The nano calcium carbonate is used as an important component of a polyethylene transparent film formula, and has great influence on the mechanical property, transparency and fluidity of a product. The transparency is a very important quality index of the polyethylene film, and the appearance, the dispersibility and the like of the nano calcium carbonate have great influence on the transparency of the filled polyethylene film. Therefore, when nano calcium carbonate is used as a filler of a polyethylene film, the quality of the polyethylene film is greatly influenced.
Patent CN 102585557a discloses a surface modification method of agricultural PE film transparent filler nano calcium carbonate. The invention adopts the silicon-aluminum composite sol to carry out wet surface treatment on the nano calcium carbonate, thereby improving the transparency of the polyethylene film filled with the nano calcium carbonate to a certain extent; however, the silicon-aluminum composite sol has cohesiveness, so that the solution viscosity is improved and the processability is extremely poor when the calcium carbonate filled polyethylene film is prepared.
The patent CN 102827400A discloses a preparation method of filling master batch for transparent polyethylene plastic film, the invention adopts rare earth coupling agent to carry out dry surface modification to heavy calcium carbonate, the process is simple, and the prepared calcium carbonate master batch has large filling amount in the polyethylene film; but there is no mention of the clarity of polyethylene film.
Patent CN 108530730a discloses a PE highly filled masterbatch doped with ultrafine calcium carbonate and a preparation method thereof, wherein the surface modification mode of calcium carbonate is as follows: adding the dried superfine calcium carbonate into a high-speed mixer, adding an ethanol solution of a titanate coupling agent KR-TTS while stirring, fully stirring, and taking out to obtain the organic surface modified superfine calcium carbonate. The modification method belongs to dry modification and is only suitable for surface modification of small-batch calcium carbonate; if the dry modification of the calcium carbonate is carried out on a large scale, the modifier is easy to disperse unevenly, so that the performance is unstable when the polyethylene is filled with the calcium carbonate.
Patent CN 109970088A discloses a preparation method of nano calcium carbonate special for high-end PE blown film, which uses oleic acid to perform surface modification on nano calcium carbonate to prepare activated nano calcium carbonate. This surface treatment reduces the frictional force when the inorganic particles are bonded to the matrix, but does not take into account the influence of the morphology and dispersion of calcium carbonate on the polyethylene film.
The patent CN 106833026a discloses a utility model relates to a transparent ultra-high strength polyethylene film, which is composed of a metallocene polyethylene layer, a polyethylene polypropylene composite layer and an ultra-high molecular weight high density polyethylene layer which are laminated in sequence. The processing method is simple and convenient, the film has high strength and low heat sealing temperature, and can ensure that the bag breaking rate of the product is reduced or the bag breaking rate is avoided, so that the packaged product is safer to transport. However, this is a way of processing the polyethylene transparent film, and is not related to the preparation of calcium carbonate suitable for the polyethylene transparent film.
In summary, there are still many problems in the preparation of the special nano calcium carbonate for polyethylene transparent films, and the existing various methods for preparing and surface modifying nano calcium carbonate still cannot well meet the requirements of polyethylene films on transparency.
Disclosure of Invention
The invention provides a preparation method of nano calcium carbonate for filling a polyethylene transparent film, aiming at the defects of the current nano calcium carbonate filler. The nano calcium carbonate particles prepared by the method have good dispersibility and complete particle appearance, and the aluminate coupling agent can be uniformly coated on the surfaces of the nano calcium carbonate particles, so that the compatibility of the nano calcium carbonate and polyethylene is enhanced; after the polyethylene film is filled with the nano calcium carbonate, the polyethylene film has high transparency, excellent mechanical property and good processability.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of nano calcium carbonate for filling a polyethylene transparent film comprises the following steps:
s1, calcining limestone at 1050-1250 ℃ to obtain quicklime, and carrying out digestion reaction on the quicklime and water to obtain Ca (OH)2Sieving and standing the mixture, and preparing the mixture into Ca (OH) with the solid content of 6.0-11.5%2A suspension;
s2 preparation of Ca (OH)2Introducing mixed gas with the carbon dioxide concentration of 20-30% into the suspension, wherein the flow rate of the mixed gas of carbon dioxide is 0.005-0.015 m2Adding monolauryl phosphate into the suspension when the pH of the reaction suspension is less than or equal to 8, stirring uniformly, and then continuously introducing carbon dioxide for reaction;
s3, when the pH value of the system is less than or equal to 7, continuously introducing the carbon dioxide mixed gas to ensure that the carbon dioxide mixed gas stably exists for 0.5-1.5h when the pH value of the reaction system is less than or equal to 7; and the carbonation reaction is continuously carried out, so that the appearance of the calcium carbonate is more regular.
And S4, adding an aluminate coupling agent solution into the suspension to carry out wet surface modification on the suspension, and finally carrying out filter pressing, drying and sieving to obtain the nano calcium carbonate for filling the polyethylene transparent film.
Preferably, the addition amount of the monolauryl phosphate is 0.15-0.5% of the dry mass of the calcium carbonate.
Preferably, the addition amount of the aluminate coupling agent solution is 5-15% of the mass of the suspension, and the mass percentage concentration of the aluminate coupling agent solution is 50%.
Preferably, the carbonation reaction in the step S2 is controlled at a temperature of 20 to 25 ℃ and a rotation speed of 600 to 900/min.
Preferably, the content of magnesium carbonate in the limestone is less than or equal to 0.2 percent.
Preferably, the surface modification is carried out at the temperature of 70-90 ℃ and the stirring speed of 300-500 r/min for 30-60 min.
Preferably, the drying is carried out at the temperature of 120-135 ℃ for 12-18 h.
Compared with the prior art, the invention has the advantages and beneficial effects that:
1. according to the method, the monolauryl phosphate is added at the later stage of the carbonation reaction, the carbon dioxide is controlled to be added at a low flow rate, the carbonation reaction is continuously carried out for 0.5-1.5h with the pH value of less than or equal to 7, and finally, the wet modification is carried out by using the aluminate coupling agent of the high treatment agent, so that the prepared nano calcium carbonate has good dispersibility, uniform particle size distribution and regular shape, the aluminate coupling agent can be uniformly coated on the surfaces of the nano calcium carbonate particles, and the compatibility of the nano calcium carbonate and polyethylene is enhanced.
2. The polyethylene film filled with the nano calcium carbonate prepared by the method has high transparency, excellent mechanical property and good processability.
Drawings
FIG. 1 is an SEM image of nano calcium carbonate prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application.
Example 1
A preparation method of nano calcium carbonate for filling a polyethylene transparent film comprises the following steps:
s1, calcining limestone with magnesium carbonate content less than or equal to 0.2% at 1100 deg.C to obtain quicklime, and carrying out digestion reaction on the quicklime and water according to grey-water ratio of 1:7 to obtain Ca (OH)2Sieving, standing, and preparing into Ca (OH) with 10% solid content2A suspension;
s2 preparation of Ca (OH)2Introducing mixed gas with carbon dioxide concentration of 20% into the suspension, wherein the flow rate of the mixed gas of carbon dioxide is 0.01m2When the pH of the reaction suspension is less than or equal to 8, adding monolauryl phosphate accounting for 0.25 percent of the dry mass of calcium carbonate into the suspension, stirring uniformly, and continuously introducing carbon dioxide for reaction, wherein the temperature is controlled at 23 ℃ and the rotating speed is 800r/min in the carbonation reaction process;
s3, when the pH value of the system is less than or equal to 7, continuously introducing the carbon dioxide mixed gas to ensure that the carbon dioxide mixed gas stably exists for 1 hour when the pH value of the reaction system is less than or equal to 7;
s4, adding 5% of aluminate coupling agent solution (mass concentration is 50%) into the suspension, stirring for 40min at the temperature of 80 ℃ and the rotating speed of 400r/min to carry out wet surface modification, finally carrying out filter pressing, drying for 15h at the temperature of 130 ℃, and sieving to obtain the nano calcium carbonate for filling the polyethylene transparent film.
The nano calcium carbonate prepared by the method is detected by a scanning electron microscope, and the test result is shown in figure 1. It can be seen from the figure that the nano calcium carbonate prepared by the invention has good dispersibility, uniform particle size distribution and regular appearance.
Example 2
A preparation method of nano calcium carbonate for filling a polyethylene transparent film comprises the following steps:
s1, calcining limestone with magnesium carbonate content less than or equal to 0.2% at 1100 deg.C to obtain quicklime, and carrying out digestion reaction on the quicklime and water according to grey-water ratio of 1:6 to obtain Ca (OH)2Sieving, standing, and formulating into Ca (OH) with 8.5% solid content2A suspension;
s2 preparation of Ca (OH)2Introducing mixed gas with carbon dioxide concentration of 25% into the suspension, wherein the flow rate of the mixed gas of carbon dioxide is 0.012m2H, when the pH of the reaction suspension is less than or equal to 8, adding monolauryl phosphate accounting for 0.3 percent of the dry mass of calcium carbonate into the suspension, stirring uniformly, and continuously introducing carbon dioxide for reaction, wherein the temperature is controlled at 24 ℃ and the rotating speed is 600r/min in the carbonation reaction process;
s3, when the pH value of the system is less than or equal to 7, continuously introducing the carbon dioxide mixed gas to ensure that the carbon dioxide mixed gas stably exists for 1.5h when the pH value of the reaction system is less than or equal to 7;
s4, adding 10% of aluminate coupling agent solution (mass concentration is 50%) into the suspension, stirring for 60min at 70 ℃ and 500r/min for wet surface modification, finally carrying out filter pressing, drying for 18h at 120 ℃, and sieving to obtain the nano calcium carbonate for filling the polyethylene transparent film.
Example 3
A preparation method of nano calcium carbonate for filling a polyethylene transparent film comprises the following steps:
s1, calcining limestone with magnesium carbonate content less than or equal to 0.2% at 1050 ℃ to obtain quicklime, and carrying out digestion reaction on the quicklime and water according to grey-water ratio of 1:6 to obtain Ca (OH)2Sieving, standing, and formulating into Ca (OH) with solid content of 7.0%2A suspension;
s2 preparation of Ca (OH)2Introducing mixed gas with carbon dioxide concentration of 22% into the suspension, wherein the flow rate of the mixed gas of carbon dioxide is 0.015m2When the pH of the reaction suspension is less than or equal to 8, adding monolauryl phosphate accounting for 0.2 percent of the dry mass of calcium carbonate into the suspension, stirring uniformly, and continuously introducing carbon dioxide for reaction, wherein the temperature is controlled at 25 ℃ and the rotating speed is 700r/min in the carbonation reaction process;
s3, when the pH value of the system is less than or equal to 7, continuously introducing the carbon dioxide mixed gas to ensure that the carbon dioxide mixed gas stably exists for 0.8h when the pH value of the reaction system is less than or equal to 7;
s4, adding 15% of aluminate coupling agent solution (mass concentration is 50%) into the suspension, stirring for 60min at 70 ℃ and 500r/min for wet surface modification, finally carrying out filter pressing, drying for 15h at 130 ℃, and sieving to obtain the nano calcium carbonate for filling the polyethylene transparent film.
Example 4
A preparation method of nano calcium carbonate for filling a polyethylene transparent film comprises the following steps:
s1, calcining limestone with magnesium carbonate content less than or equal to 0.2% at 1200 ℃ to obtain quicklime, and carrying out digestion reaction on the quicklime and water according to grey-water ratio of 1:8 to obtain Ca (OH)2Sieving, standing, and formulating into Ca (OH) with 10.5% solid content2Suspended in waterLiquid;
s2 preparation of Ca (OH)2Introducing mixed gas with carbon dioxide concentration of 30% into the suspension, wherein the flow rate of the mixed gas of carbon dioxide is 0.01m2When the pH of the reaction suspension is less than or equal to 8, adding monolauryl phosphate accounting for 0.3 percent of the dry mass of calcium carbonate into the suspension, stirring uniformly, and continuously introducing carbon dioxide for reaction, wherein the temperature is controlled at 25 ℃ and the rotating speed is 600r/min in the carbonation reaction process;
s3, when the pH value of the system is less than or equal to 7, continuously introducing the carbon dioxide mixed gas to ensure that the carbon dioxide mixed gas stably exists for 1.2h when the pH value of the reaction system is less than or equal to 7;
s4, adding 12 percent of aluminate coupling agent solution (mass concentration is 50 percent) into the suspension, stirring for 60min at the temperature of 70 ℃ and the rotating speed of 500r/min for wet surface modification, finally carrying out filter pressing, drying for 18h at the temperature of 120 ℃, and sieving to obtain the nano calcium carbonate for filling the polyethylene transparent film.
Comparative example 1
S1, calcining limestone with magnesium carbonate content less than or equal to 0.2% at 1200 ℃ to obtain quicklime, and carrying out digestion reaction on the quicklime and water according to grey-water ratio of 1:8 to obtain Ca (OH)2Sieving, standing, and formulating into Ca (OH) with 10.5% solid content2A suspension;
s2 preparation of Ca (OH)2Introducing mixed gas with carbon dioxide concentration of 30% into the suspension, wherein the flow rate of the mixed gas of carbon dioxide is 0.01m2When the pH of the reaction suspension is less than or equal to 8, adding monolauryl phosphate accounting for 0.3 percent of the dry mass of calcium carbonate into the suspension, stirring uniformly, and continuously introducing carbon dioxide for reaction, wherein the temperature is controlled at 25 ℃ and the rotating speed is 600r/min in the carbonation reaction process;
s3, when the pH value of the system is less than or equal to 7, adding 12% of aluminate coupling agent solution (mass concentration is 50%) into the suspension, stirring for 60min at 70 ℃ and 500r/min for wet surface modification, finally carrying out filter pressing, drying for 18h at 120 ℃, and sieving to obtain the nano calcium carbonate.
Comparative example 2
S1 calcining limestone with magnesium carbonate content less than or equal to 0.2% at 1200 deg.CObtaining quicklime, and obtaining Ca (OH) by the digestion reaction of the quicklime and water according to the grey water ratio of 1:82Sieving, standing, and formulating into Ca (OH) with 10.5% solid content2A suspension;
s2 preparation of Ca (OH)2Introducing mixed gas with carbon dioxide concentration of 30% into the suspension, wherein the flow rate of the mixed gas of carbon dioxide is 0.01m2When the pH of the reaction suspension is less than or equal to 8, adding monolauryl phosphate accounting for 0.3 percent of the dry mass of calcium carbonate into the suspension, stirring uniformly, and continuously introducing carbon dioxide for reaction, wherein the temperature is controlled at 25 ℃ and the rotating speed is 600r/min in the carbonation reaction process;
s3, when the pH value of the system is less than or equal to 7, continuously introducing carbon dioxide mixed gas to ensure that the reaction system stably exists for 1.2h under the condition that the pH value is less than or equal to 7, finally, performing filter pressing, drying for 18h at the temperature of 120 ℃, and sieving to obtain the nano calcium carbonate.
Comparative example 3
S1, calcining limestone with magnesium carbonate content less than or equal to 0.2% at 1200 ℃ to obtain quicklime, and carrying out digestion reaction on the quicklime and water according to grey-water ratio of 1:8 to obtain Ca (OH)2Sieving, standing, and formulating into Ca (OH) with 10.5% solid content2A suspension;
s2 preparation of Ca (OH)2Introducing mixed gas with carbon dioxide concentration of 30% into the suspension, wherein the flow rate of the mixed gas of carbon dioxide is 0.01m2When the pH of the reaction suspension is less than or equal to 8, controlling the temperature to be 25 ℃ and the rotating speed to be 600r/min in the carbonation reaction process;
s3, when the pH value of the system is less than or equal to 7, continuously introducing the carbon dioxide mixed gas to ensure that the carbon dioxide mixed gas stably exists for 1.2h when the pH value of the reaction system is less than or equal to 7;
s4, adding 12 percent aluminate coupling agent solution into the suspension, stirring for 60min at the temperature of 70 ℃ and the rotating speed of 500r/min for wet surface modification, finally carrying out filter pressing, drying for 18h at the temperature of 120 ℃, and sieving to obtain the nano calcium carbonate.
The nano calcium carbonate prepared in examples 1 to 4 of the present invention and comparative examples 1 to 3 was used to prepare a polyethylene transparent film according to the formulation shown in table 1. The preparation method of the polyethylene transparent film comprises the following steps: weighing the components according to the formula proportion, adding the components into a mixer of a high-speed stirrer, mixing the nano calcium carbonate at the rotating speed of 1000r/min at 100 ℃ for 10min, and removing moisture; then adding LDPE, white oil and paraffin wax, and stirring for 5min at the rotating speed of 1000 r/min; then adding stearic acid, stirring for 15 minutes and discharging. Adding the mixed materials into a double-screw extruder, and gradually increasing the temperature of each area to 130-170 ℃; extrusion and feeding are set to be 40 r/min; finally obtaining extruded strips, air-drying and granulating to obtain the particles for the polyethylene film. Adding the polyethylene film particles into a film blowing machine, and gradually increasing the temperature to 165-180 ℃ in each zone to prepare the polyethylene film with the width of 13mm and the thickness of 0.04 mm.
Table 1: the formula of the nano calcium carbonate polyethylene transparent film
| Name (R) | Number of parts |
| LDPE | 100 |
| Stearic acid | 0.5 |
| Paraffin wax | 0.35 |
| White oil | 0.1 |
| Nano calcium carbonate | 20 |
The properties of the polyethylene film, polyethylene film transparency test, were determined as follows: measured by a whiteness tester YQ-Z-48B of the building materials in use, light industrial automation research institute, Inc. Testing the mechanical properties of the polyethylene film: the measurement is carried out by using a universal testing machine UTM6104 of Shenzhen Sansi longitudinal and transverse Limited. Melt index test: measured using a underwriters longitudinal relaxation testing apparatus, Inc. melt flow Rate apparatus XNR-400B.
Table 2: the performance test result of the application of the nano calcium carbonate in the polyethylene film
| Name (R) | Degree of transparency% | Transverse tensile Property, MPa | Longitudinal tensile property, MPa | Melt index, g/10min |
| Example 1 | 89.4 | 32.4 | 42.5 | 6.3 |
| Example 2 | 91.2 | 39.1 | 47.3 | 7.9 |
| Example 3 | 91.8 | 41.5 | 49.7 | 8.5 |
| Example 4 | 90.7 | 39.6 | 48.2 | 8.3 |
| Comparative example 1 | 86.7 | 37.6 | 44.5 | 8.2 |
| Comparative example 2 | 83.5 | 27.3 | 36.1 | 7.2 |
| Comparative example 3 | 85.7 | 25.0 | 38.9 | 6.9 |
From the test results, the nano calcium carbonate filled polyethylene film prepared by the method disclosed by the invention has the advantages of high transparency, excellent mechanical properties and good processability.
The foregoing is a more detailed description of the invention in connection with specific/preferred embodiments and is not intended to limit the practice of the invention to those descriptions. It will be apparent to those skilled in the art that various substitutions and modifications can be made to the described embodiments without departing from the spirit of the invention, and such substitutions and modifications are to be considered as within the scope of the invention.
Claims (7)
1. A preparation method of nano calcium carbonate for filling a polyethylene transparent film is characterized by comprising the following steps: the method comprises the following steps:
s1, calcining limestone at 1050-1250 ℃ to obtain quicklime, and carrying out digestion reaction on the quicklime and water to obtain Ca (OH)2Sieving and standing the mixture, and preparing the mixture into Ca (OH) with the solid content of 6.0-11.5%2A suspension;
s2 preparation of Ca (OH)2Introducing mixed gas with the carbon dioxide concentration of 20-30% into the suspension, wherein the flow rate of the mixed gas of carbon dioxide is 0.005-0.015 m2Adding monolauryl phosphate into the suspension when the pH of the reaction suspension is less than or equal to 8, stirring uniformly, and then continuously introducing carbon dioxide for reaction;
s3, when the pH value of the system is less than or equal to 7, continuously introducing the carbon dioxide mixed gas to ensure that the carbon dioxide mixed gas stably exists for 0.5-1.5h when the pH value of the reaction system is less than or equal to 7;
and S4, adding an aluminate coupling agent solution into the suspension to carry out wet surface modification on the suspension, and finally carrying out filter pressing, drying and sieving to obtain the nano calcium carbonate for filling the polyethylene transparent film.
2. The method for preparing nano calcium carbonate for filling a polyethylene transparent film according to claim 1, which is characterized in that: the addition amount of the monolauryl phosphate is 0.15-0.5% of the dry mass of the calcium carbonate.
3. The method for preparing nano calcium carbonate for filling a polyethylene transparent film according to claim 1, which is characterized in that: the adding amount of the aluminate coupling agent solution is 5-15% of the mass of the suspension, and the mass percentage concentration of the aluminate coupling agent solution is 50%.
4. The method for preparing nano calcium carbonate for filling a polyethylene transparent film according to claim 1, which is characterized in that: in step S2, the carbonation reaction is controlled at a temperature of 20 to 25 ℃ and a rotational speed of 600 to 900/min.
5. The method for preparing nano calcium carbonate for filling a polyethylene transparent film according to claim 1, which is characterized in that: the content of magnesium carbonate in the limestone is less than or equal to 0.2 percent.
6. The method for preparing nano calcium carbonate for filling a polyethylene transparent film according to claim 1, which is characterized in that: the surface modification is to stir for 30-60 min at the temperature of 70-90 ℃ and the rotating speed of 300-500 r/min.
7. The method for preparing nano calcium carbonate for filling transparent polyethylene film according to claim, wherein the method comprises the following steps: the drying is carried out at the temperature of 120-135 ℃ for 12-18 h.
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