CN112724512A - Preparation method of nano-cellulose polypropylene master batch - Google Patents
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C08J2401/02—Cellulose; Modified cellulose
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
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Abstract
The invention relates to a preparation method of a nano-cellulose polypropylene master batch, belonging to the field of high polymer materials. The invention adopts a simple and easy way, takes the common filler in PP plastic as a medium, loads the nano-cellulose on the medium, and then prepares the nano-cellulose and PP into a master batch. The inorganic fillers tend to be small in size and negatively charged on the surface, and repel nanocellulose also negatively charged, so that the presence of these fillers acts to prevent the nanocellulose from agglomerating, allowing the nanocellulose to be well dispersed in the PP in the subsequent step. The nano-cellulose can be used for modifying PP plastics on a large scale on the premise of not changing the forming process of PP products.
Description
Technical Field
The invention relates to a preparation method of a nano-cellulose polypropylene master batch, belonging to the field of high polymer materials.
Background
Polypropylene (PP) is one of the largest plastics used in the world due to its advantages of low density, good electrical insulation, chemical corrosion resistance, fatigue resistance, and easy processing, and is widely used in the fields of automobiles, packaging industry, pipe fittings, daily necessities, and the like. Meanwhile, the consumption of PP plastic always stays at the first level of plastic for vehicles. However, since PP has problems such as poor low-temperature toughness in mechanical properties, studies on the modification of PP have been carried out along with the progress of its application. In the field of automobiles, the influence of PP on the aspects of environmental protection and energy conservation (light weight of automobiles) is particularly noticed when the PP is subjected to mechanical modification, so that the material with the characteristics of environmental protection has the advantage of being unique when the reinforced modified material is selected.
The nano-cellulose is a green reinforced material with the renewable and degradable characteristics of cellulose, high specific modulus and high specific strength, and the application of the nano-cellulose in polypropylene modification is a new hot spot in the field in recent years. However, the uniform dispersion of hydrophilic nanocellulose in PP is always a bottleneck problem hindering its application.
The literature reports methods for dispersing nanocellulose in thermoplastic polymers mainly include: (1) the nano-cellulose suspension is first spray dried or freeze dried into dry powder, and the nano-scale is maintained as far as possible, and then added during the plastic extrusion and granulation process. Because the dried nano-cellulose is easy to agglomerate through the action of hydrogen bonds, the nano-cellulose can not be uniformly dispersed in PP (shown in figure 1) by the method, so that the mechanical property of the obtained nano-cellulose/PP composite material is reduced compared with that of pure PP, wherein the tensile strength of the modified PP added with 5% of nano-cellulose is reduced by 6.2% and the elongation at break is reduced by 11.8% compared with that of the pure PP; (2) carrying out hydrophobic modification on the nanocellulose through a series of complex chemical reactions; (3) solvent replacement is carried out to disperse the nano-cellulose water suspension into a strong polar organic solvent, simultaneously dissolve the polymer into the same kind of organic solvent to prepare a solution, then uniformly mix the two solutions, and remove the solvent through evaporation to obtain the mixture of the nano-cellulose and the thermoplastic polymer. The common problems of the methods are that the operation process is complex, time-consuming and labor-consuming; in addition, a large amount of organic solvent is required in some operation processes, so that the risk of environmental pollution is increased; some operation processes (such as freeze drying) have high cost, are only suitable for small-batch application in a laboratory, and are difficult to adapt to the requirements of large-batch industrial production.
Talcum powder, calcium carbonate, mica powder, kaolin, silica, graphite, carbon black, halogen-free flame retardants (magnesium hydroxide, aluminum hydroxide and the like) and the like are commonly used fillers in the formula of polypropylene plastics. The invention takes the fillers as media, firstly loads the nano-cellulose on the fillers, and prepares the PP master batch on the basis. The master batch can be applied to PP modification in a large scale, and the realization process is simple and easy to operate.
Disclosure of Invention
The invention aims to provide a preparation method of a nano-cellulose polypropylene master batch. The method adopts a simple and feasible mode, takes the common filler in PP plastic as a medium, loads the nano-cellulose on the medium, and then prepares the nano-cellulose and PP into a master batch. The nano-cellulose can be used for modifying PP plastics on a large scale on the premise of not changing the forming process of PP products.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a nano-cellulose polypropylene master batch comprises the following steps:
(1) adding the metered PP filler into the nano cellulose suspension subjected to ultrasonic dispersion, uniformly stirring and mixing, and drying the mixture at the temperature of (105 +/-2) ℃ to constant weight to obtain a mixture 1 of the filler and the nano cellulose;
(2) dispersing and mixing the mixture 1 and PP in a high-speed mixer to obtain a mixed raw material 2;
(3) and (3) mixing and granulating the raw material 2 in an internal mixer or a single/double screw extruder to obtain the nano-cellulose polypropylene master batch.
In the method, the mass ratio of the filler to the nanocellulose (dry weight) in the step (1) is more than 1:1, and the mass ratio of the PP to the nanocellulose (dry weight) is more than 1: 1;
in the above method, the filler selected in step (1) includes, but is not limited to, common PP inorganic fillers such as talc, calcium carbonate, silica, carbon black, and the like. Different from the dispersion mechanism of the nano-cellulose on the biomass filler (depending on the similarity of the nano-cellulose and the biomass filler), the inorganic fillers are usually small in size and have negative charges on the surface, and the inorganic fillers are mutually repulsive to the nano-cellulose with the same negative charges, so that the presence of the fillers can play a role in preventing the nano-cellulose from agglomerating, and the nano-cellulose can be well dispersed in the PP in the subsequent step.
In the above method, the process conditions for kneading and granulating in an internal mixer or a single/twin screw extruder in the step (3) are the same as those in the case where no nanocellulose is added.
Advantageous effects
1. The invention provides a preparation method of a nano-cellulose polypropylene master batch. The method is simple and easy to implement and low in cost, and adopts the common filler in PP plastic as a medium, and firstly, the nano cellulose is loaded on the medium, and then the nano cellulose and the PP are made into a master batch. The invention can add the nano-cellulose into the PP product formula in the form of master batch without changing the PP molding process, thereby perfectly solving the problem of dispersion of the nano-cellulose in PP.
2. On the basis, the mechanical property of the PP added with the nano-cellulose is improved, and the purposes of reducing the material and the weight can be achieved when a PP product is designed, so that the application advantages of the PP product on vehicles such as automobiles and airplanes are particularly obvious. The reason is that the weight reduction of automobiles and airplanes directly brings down the energy consumption of fuel and the like, which has very positive contribution to energy conservation and environmental protection.
3. Compared with the methods reported in the past documents, the method provided by the invention can obviously reduce the molding processing cost on the premise of meeting the performance requirements, can be completed only by conventional polypropylene processing equipment, and is a method suitable for industrial mass production.
4. Unlike the dispersion mechanism of the nanocellulose on the biomass filler (the nanocellulose and the biomass filler are similar in structure), the inorganic fillers are usually small in size and have negative charges on the surface, and the inorganic fillers are mutually repulsive to the nanocellulose with the negative charges, so that the presence of the fillers can play a role in preventing the nanocellulose from agglomerating, and the nanocellulose can be well dispersed in the PP in the later step.
Drawings
FIG. 1 is a scanning electron microscope image of an impact section of a nanocellulose/PP composite material prepared by directly adding dried nanocellulose to PP;
FIG. 2 is a scanning electron microscope image of an impact section of a modified PP specimen 1 prepared by adding a nano-cellulose polypropylene master batch in example 1 of the present invention;
FIG. 3 is a perspective view of the modified PP specimen 2 prepared by adding nano-cellulose polypropylene master batch in example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
Example 1
A preparation method of a nano-cellulose polypropylene master batch comprises the following specific steps:
(1) 200g of talcum powder is poured into the nano-cellulose water suspension after ultrasonic treatment, and the nano-cellulose water suspension is stirred for 1h, wherein the dry weight of the nano-cellulose is about 60 g. Drying the mixture at 105 +/-2 ℃ to obtain a mixture 1 of the talcum powder and the nano-cellulose;
(2) dispersing and mixing the mixture 1 and 400g of polypropylene in a high-speed mixer to obtain a mixed raw material 2;
(3) mixing and granulating the raw material 2 in a single-screw extruder to obtain a nano-cellulose polypropylene master batch;
(4) mixing and dispersing the nano-cellulose polypropylene master batch with 1400g of PP and 60g of MAPP in a high-speed mixer according to a pre-designed PP formula, extruding and granulating in a single-screw extruder, and performing injection molding to obtain a modified PP sample 1. The mechanical property data of PP before and after modification at room temperature are shown in Table 1.
TABLE 1 mechanical Properties of PP specimen 1 before and after modification
As can be seen from Table 1, the mechanical properties of PP are significantly improved after the nanocellulose is added, because the nanocellulose is well dispersed in PP (see figure 2).
Example 2
A preparation method of a nano-cellulose polypropylene master batch comprises the following specific steps:
(1) pouring 40g of talcum powder into the nano-cellulose water suspension after ultrasonic treatment, and stirring for 30min, wherein the dry weight of the nano-cellulose is 40 g. Drying the mixture at 105 +/-2 ℃ to obtain a mixture 1 of the talcum powder and the nano-cellulose;
(2) dispersing and mixing the mixture 1 and 40g of polypropylene in a high-speed mixer to obtain a mixed raw material 2;
(3) mixing and granulating the raw material 2 in a double-screw extruder to obtain a nano-cellulose polypropylene master batch;
(4) mixing and dispersing the nano-cellulose polypropylene master batch with 260g of talcum powder, 1460g of PP, 300g of POE and 40g of MAPP in a high-speed mixer according to a pre-designed PP formula, extruding and granulating in a double-screw extruder, and then carrying out injection molding to obtain a modified PP sample 2. The mechanical property data of PP before and after modification at room temperature are shown in Table 2.
TABLE 2 mechanical Properties of PP specimen 2 before and after modification
As can be seen from Table 2, the mechanical properties of PP are improved by adding nanocellulose, since nanocellulose is well dispersed in PP (see figure 3).
The above detailed description is intended to illustrate the objects, aspects and advantages of the present invention, and it should be understood that the above detailed description is only exemplary of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (3)
1. A preparation method of a nano-cellulose polypropylene master batch is characterized by comprising the following steps: the method comprises the following steps:
step one, adding a measured PP filler into a nano cellulose suspension subjected to ultrasonic dispersion, uniformly stirring and mixing, and drying at the temperature of (105 +/-2) DEG C to constant weight to obtain a mixture 1 of the filler and the nano cellulose;
step two, dispersing and mixing the mixture 1 and PP in a high-speed mixer to obtain a mixed raw material 2;
mixing and granulating the mixed raw material 2 in an internal mixer or a single/double screw extruder to obtain nano cellulose polypropylene master batch;
the mass ratio of the filler to the nanocellulose (dry weight) is above 1:1, and the mass ratio of the PP to the nanocellulose (dry weight) is above 1: 1.
2. The method for preparing a nano-cellulose polypropylene master batch as claimed in claim 1, wherein the method comprises the following steps: the filler is an inorganic filler; the inorganic fillers are small in size and negatively charged on the surface, and repel nanocellulose which is also negatively charged, so that the presence of these fillers can prevent the nanocellulose from agglomerating, and the nanocellulose can be well dispersed in PP in the subsequent step.
3. The method for preparing a nano-cellulose polypropylene master batch as claimed in claim 1, wherein the method comprises the following steps: the inorganic filler includes, but is not limited to, talc, calcium carbonate, silica, and carbon black.
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Cited By (3)
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| CN113180275A (en) * | 2021-05-13 | 2021-07-30 | 湖北中烟工业有限责任公司 | Tobacco sheet by rolling method and preparation method thereof |
| CN113980391A (en) * | 2021-12-09 | 2022-01-28 | 北京理工大学 | Nano cellulose plastic additive, reinforced polypropylene material and preparation method |
| CN115926318A (en) * | 2022-12-27 | 2023-04-07 | 浙江新浪包装有限公司 | Environment-friendly plastic woven bag and preparation method thereof |
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Cited By (3)
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| CN113980391A (en) * | 2021-12-09 | 2022-01-28 | 北京理工大学 | Nano cellulose plastic additive, reinforced polypropylene material and preparation method |
| CN115926318A (en) * | 2022-12-27 | 2023-04-07 | 浙江新浪包装有限公司 | Environment-friendly plastic woven bag and preparation method thereof |
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