CN116162305A - Special nano composite auxiliary agent for tape-casting linear low-density polyethylene anti-adhesive resin and preparation method thereof - Google Patents

Special nano composite auxiliary agent for tape-casting linear low-density polyethylene anti-adhesive resin and preparation method thereof Download PDF

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CN116162305A
CN116162305A CN202210643085.XA CN202210643085A CN116162305A CN 116162305 A CN116162305 A CN 116162305A CN 202210643085 A CN202210643085 A CN 202210643085A CN 116162305 A CN116162305 A CN 116162305A
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density polyethylene
linear low
auxiliary agent
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曾舒
张怡
黄晓枭
王聚恒
陈文�
曾化雨
陈磊
刘蔚凯
麻玉龙
杨康
钟安澜
钟颜阳
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GUIZHOU NANO MATERIAL ENGINEERING CENTER
Guizhou Tianrunda Science And Technology Co ltd
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GUIZHOU NANO MATERIAL ENGINEERING CENTER
Guizhou Tianrunda Science And Technology Co ltd
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/24—Crystallisation aids

Abstract

The invention relates to a special nano composite auxiliary agent for a casting linear low-density polyethylene anti-adhesive resin and a preparation method thereof, wherein the preparation technology comprises the following steps: 1) Uniformly mixing the rheological additive, the anti-sticking agent, the inorganic nano adsorption-nucleating agent and the yellow index control agent by using a high-speed stirring device to perform; 2) Uniformly reinforcing the preformed component and other components into a composite material by adopting a gravity-free mixing device; 3) And curing the composite material at low temperature through parallel double screws, and finally obtaining the composite additive with uniform size through a granule pressing forming and screening device. The composite auxiliary agent can promote the cast linear low-density polyethylene anti-adhesive special resin to obtain the cast polyethylene thin with excellent comprehensive properties such as good optical, mechanical and anti-adhesive properties, and the like, scientifically solves the problems of accurate regulation and control of dust-free environment in the preparation process of the nano composite auxiliary agent and dust-free addition of the composite auxiliary agent in the production process of the special material for the polyethylene resin, and is a special high-performance nano functional composite auxiliary agent for the linear low-density polyethylene cast resin.

Description

Special nano composite auxiliary agent for tape-casting linear low-density polyethylene anti-adhesive resin and preparation method thereof
Technical Field
The invention relates to a special nano composite auxiliary agent for a casting linear low-density polyethylene anti-adhesive resin, belonging to the field of multifunctional composite auxiliary agents for polymers.
Background
The polyethylene packaging film mainly comprises three molding processes of blow molding, tape casting and biaxial stretching. Compared with the traditional blow molding method, the casting method has the advantages of high production speed, high yield, good film optics, good thickness uniformity, easier composite printing, lower cost than the biaxial stretching method, simple equipment and good heat sealing performance. Therefore, the cast polyethylene packaging film is particularly suitable for the packaging fields of foods, medicines, clothes, flowers, daily chemicals and the like with higher requirements on heat sealing and optical performance of packaging materials. The cast polyethylene film is mainly produced by taking linear low-density polyethylene resin as a raw material.
The three-layer co-extrusion is a main production process of the cast polyethylene film, and the three-layer co-extrusion cast film structure is generally divided into three layers of a corona layer, a core layer and a heat sealing layer from outside to inside, and resin raw materials meeting the requirements of all the layers can be independently selected to endow the film with different properties and purposes. The linear low density polyethylene resin with anti-adhesive function is a common resin for a corona layer and a core layer of Cast Polyethylene (CPE).
At present, the problems of the special anti-adhesive tape casting linear low-density polyethylene resin material mainly exist as follows: due to the linear low-density polyethylene resin synthesis system, the molecular weight distribution is narrower, and the apparent crystal points of the film used for the casting process are easy to appear; the traditional anti-thermal oxidation aging system can not meet the conditions that the section of the film is yellow or red due to the high-temperature casting process, and the transparency and the glossiness are poor due to the fact that the content of the traditional antioxidant is increased; the casting (non-inflation) process film is easy to adhere and difficult to open, and the like, so that the problems can be solved, the physical properties of the base materials can be optimized through the polymer production process of petrochemical enterprises, but the method is limited by devices and technologies, has limited regulation and control range and high cost, and therefore, the method for modifying the polymer by adding the multifunctional integrated composite auxiliary agent in the granulating stage for blending is a general polymer modification method which is convenient to operate, has proper cost and wider adjustable range.
In recent years, the nanomaterial is widely applied to the field of functional polymer material modification by virtue of unique physical and chemical property advantages such as surface interface effect, small size effect and quantum size effect.
Disclosure of Invention
The invention aims to provide a nano composite additive special for a tape casting linear low-density polyethylene anti-adhesive resin and a preparation method thereof. The composite additive is used for producing the special material for the casting linear low-density polyethylene anti-adhesive resin, and the casting linear low-density polyethylene film with excellent comprehensive properties such as good optics, mechanics, anti-adhesive, processing molding, thermal oxidation aging resistance and the like can be obtained.
The nano composite auxiliary agent has the characteristics of integration, easy addition, small addition amount, low-temperature preparation and the like, and scientifically solves the problems of accurate regulation and control of dust-free environment in the preparation process of the nano composite auxiliary agent and dust-free addition of the composite auxiliary agent in the production process of the anti-adhesion linear low-density polyethylene resin special material.
The aim of the invention is achieved by the following technical scheme, wherein the raw material percentages are mass percentages except for special descriptions.
The invention comprises the following components:
Figure RE-GDA0003873602960000021
the anti-sticking agent is one or a mixture of more than two of spherical silicon dioxide, spherical barium sulfate, flaky talcum powder and flaky calcium carbonate with the particle size of 3-10 microns.
The compound antioxidant is one or a mixture of more than two of phenolic antioxidants (1010, 1076, 300, 3114, etc.) and phosphite antioxidants (168, 626, etc.).
The inorganic nano adsorption-nucleating agent is one or a mixture of more than two of organic modified nano silicon dioxide, organic modified nano titanium dioxide, organic modified nano barium sulfate and organic modified nano calcium carbonate in any proportion.
The acid absorbing stabilizer is one or a mixture of more than two of calcium stearate, zinc stearate, magnesium stearate and hydrotalcite in any proportion.
The rheological aid is one or a mixture of more than two of ethylene bisstearamide and derivatives thereof, ethylene hydroxystearamide and derivatives thereof, stearic acid and alkali metal and alkaline earth metal salts thereof, hydroxystearic acid and alkali metal and alkaline earth metal salts thereof and fluorine-containing polymer PPA in any proportion.
The yellow finger control agent has a molecular formula of Na 6 Al 4 Si 6 S 4 O 20 One or two of nano inorganic ultramarine blue and ultramarine violet pigments in any proportion.
The invention relates to a preparation method of a nano composite auxiliary agent special for a tape-casting linear low-density polyethylene anti-adhesive resin, which comprises the following steps:
1) The rheological auxiliary agent, the anti-adhesion agent, the inorganic nano adsorption-nucleating agent and the yellow index control agent are uniformly mixed and preformed by utilizing a double-screw high-speed stirring device capable of realizing dust-free environment regulation. The process comprises the following steps: the rotating speed is 100-130rpm, the temperature is controlled at 75-85 ℃, and the stirring time is 20-35min;
2) Uniformly reinforcing the preformed component and other components into a composite material by adopting a double-shaft paddle gravity-free mixing device capable of realizing dust-free environment regulation; the process comprises the following steps: the rotating speed is 40-60rpm, the temperature is controlled at 75-85 ℃, and the stirring time is 30-40min;
3) And curing the composite material at low temperature through parallel double screws, and finally obtaining the columnar composite additive with uniform size through a granule pressing forming and screening device. The process comprises the following steps: the temperature is controlled to be 50-90 ℃, the rotating speed of a screw is controlled to be 0.2-0.45 ton/hour, the rotating speed of a tooth machine is controlled to be 0.2-0.45 ton/hour, the particle size of a screening device is controlled to be 2-4mm, and the particle size of the composite additive is controlled to be 5-7 g/particle.
The preparation method of the composite additive comprises the following steps: firstly, preforming and uniformly mixing all components by utilizing a solid-phase polymerization device; secondly, adopting a gravity-free mixing device to strengthen uniformity of each component; and curing and forming the composite material by using parallel double screws, and finally obtaining the columnar composite additive with uniform size by using a tooth aligning machine and a screening device. Table 1 shows some of the physical indices of the adjuvants of the invention:
TABLE 1
Project Index (I)
Drying weight loss (105)/DEG C 0.3-0.5
Oil absorption value (g/100 g) 70
Loss of weight due to burning (850 ℃ C.)/% 30-35
Appearance of Light blue columnar particles
Smell of Fresh taste
Particle size/mm 2-4
Length/mm 4-5
The applicant applies the invention to the modification of resins such as random copolymer polypropylene and the like to promote the comprehensive performance of the polypropylene after the modification to meet the international high demand, and the table 2 is the test data of the polypropylene product after the modification by the invention:
TABLE 2
Figure RE-GDA0003873602960000041
As is clear from Table 2, the impact strength of the polyethylene product added with the product is obviously increased, and the strength, toughness and temperature resistance of the polyethylene product are improved to a great extent.
The technical scheme provided by the invention has the beneficial effects that:
the linear low-density polyethylene resin is taken as a base material, an integrated functional nano composite auxiliary agent is adopted, the optical, mechanical, anti-adhesion, processing and molding performances, thermo-oxidative aging resistance and other performances of a film product are comprehensively improved, the difficulty of adding the auxiliary agent in the production process of the special material for the casting linear low-density polyethylene resin is solved, and meanwhile, the comprehensive performance of the casting polyethylene film is remarkably improved:
(1) Optical, anti-sticking, processing rheology synergy: the complex application of the inorganic nano adsorption-nucleating agent, the anti-adhesion agent and the rheological agent breaks through the difficulty that the optical performance, the anti-adhesion performance and the processing rheological performance of the film are difficult to be compatible, obviously improves the transparency and the glossiness of the film, increases the processing fluidity, effectively inhibits the phenomena of shark slices and false crystal points of the product and improves the dispersibility of the anti-adhesion agent.
(2) Thermal oxidative aging resistance: the oxidation induction period is prolonged by more than 1 time by compounding various hindered phenols and phosphite antioxidants, and meanwhile, the inorganic nano yellow finger control agent is introduced, so that the color and luster of the film are kept bright by double effects, and the problem that the resin is easy to age and yellow due to high processing temperature is solved.
(3) Improving apparent crystal point of the film: and (3) continuously carrying out polymerization reaction on catalyst residual sites to form transition polymers and apparent crystal points in the secondary processing of catalyst residual sites in the production process of the cast polyethylene special resin, and selecting modified inorganic nano materials with higher temperature resistance for targeted adsorption according to the production process of the resin and the production characteristics of the cast polyethylene film so as to ensure that the residual catalyst is adsorbed, wrapped or passivated.
(4) The low-temperature forming process comprises the following steps: the apparent density of the nano material is reduced by adopting a preforming process and the nano material is mixed without gravity, so that the technical difficulties of uniform mixing of multi-component composite additives such as different granularity, apparent density, physicochemical property, specific surface energy and the like are solved; the low-temperature extrusion and pelleting process of the parallel double-screw extruder is adopted to realize complete retention of the performance of the thermosensitive functional components, and the productivity is improved by more than 3 times of that of the common molding technology.
Drawings
Fig. 1 is a diagram of a technical scheme for implementing the present invention.
Note that: the process flow diagram is shown in the attached drawings.
The preparation method of the composite additive comprises the following steps: firstly, preforming and uniformly mixing all components by utilizing a solid-phase polymerization device; secondly, adopting a gravity-free mixing device to strengthen uniformity of each component; and curing and forming the composite material by using parallel double screws, and finally obtaining the columnar composite additive with uniform size by using a tooth aligning machine and a screening device.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be illustrative only and not limiting in scope, and those skilled in the art or researchers can make many corresponding improvements and adaptations based on the present invention.
Example 1
The nanometer functional composite auxiliary agent special for the tape-casting linear low-density polyethylene anti-adhesive resin comprises the following components in percentage by mass: 20% of an antioxidant (168), 10% of an antioxidant (1010), 2% of a dispersing agent, 8% of a heat stabilizer, 1% of an antistatic agent, 1.2% of an ultraviolet-resistant absorbent, 8% of an adhesive, 21% of inorganic nano functional particle calcium carbonate and 0.05% of an anti-yellowing agent. Sequentially placing the raw materials of the components into a solid-phase polymerization device and stirring for 30min; stirring in a gravity-free mixer for 30min; and preparing the columnar composite additive through a parallel double-screw extruder, a tooth aligning machine and a screening device. The composite additive and the random polypropylene resin are mixed according to the mass ratio of 0.45 percent: 1 are evenly mixed, extruded and granulated by a double screw extruder at the processing temperature of 180-220 ℃, and then a three-layer casting machine is utilized to cast a film (a corona layer and a core layer are LLDPE-7042, and a heat sealing layer is a self-made master batch) for testing.
The polypropylene films were tested for optical, friction, tensile properties, heat distortion temperature and after irradiation (40 KGy) yellow index, respectively, with reference to GB/T2410-2008, GB/T10006-1988, GB/T13022-1991, GB/T1043-2008, GB/T1634-2019 and GB/T2409-1980.
Example 2
The nanometer functional composite auxiliary agent special for the tape-casting linear low-density polyethylene anti-adhesive resin comprises the following components in percentage by mass: 20% of an antioxidant (168), 20% of an antioxidant (1010), 5% of a dispersing agent, 10% of a heat stabilizer, 1.5% of an antistatic agent, 1.5% of an ultraviolet-resistant absorbent, 12% of an adhesive, 27% of inorganic nano functional particle barium sulfate and 0.06% of an anti-yellowing agent. Sequentially placing the raw materials of the components into a solid-phase polymerization device and stirring for 30min; stirring in a gravity-free mixer for 30min; and preparing the columnar composite additive through a parallel double-screw extruder, a tooth aligning machine and a screening device.
Example 3
The nanometer functional composite auxiliary agent special for the tape-casting linear low-density polyethylene anti-adhesive resin comprises the following components in percentage by mass: 15% of antioxidant (168), 15% of antioxidant (1010), 4% of dispersing agent, 5% of heat stabilizer, 2% of antistatic agent, 1.0% of anti-ultraviolet absorber, 10% of adhesive, 15% of inorganic nano functional particle calcium carbonate, 15% of inorganic nano functional particle barium sulfate and 0.09% of anti-yellowing agent. Sequentially placing the raw materials of the components into a solid-phase polymerization device and stirring for 30min; stirring in a gravity-free mixer for 30min; and preparing the columnar composite additive through a parallel double-screw extruder, a tooth aligning machine and a screening device.
TABLE 3 optical, thermal and mechanical Properties test of 0.04mm Plastic film
Figure RE-GDA0003873602960000061
As shown by the test result data in the table 3, the composite additive remarkably improves the mechanical property, the thermal deformation temperature, the yellow index after radiation (40 KGy) and the processability of the linear low-density polyethylene resin, and remarkably reduces the haze of the film. The film samples of each example do not have the apparent crystal point problem of the film.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments disclosed herein. It will be understood by those skilled in the art that various changes in detail may be effected therein without departing from the scope of the invention as defined by the claims appended hereto.

Claims (12)

1. The nano composite auxiliary agent special for the tape casting linear low density polyethylene anti-adhesive resin is mainly characterized by comprising the following formula components in percentage by mass:
Figure RE-FDA0003873602950000011
2. the nano composite assistant for the anti-sticking resin of the casting linear low density polyethylene according to claim 1, which is characterized in that the anti-sticking agent is one or a mixture of more than two of spherical silicon dioxide, spherical barium sulfate, flaky talcum powder and flaky calcium carbonate with the particle size of 2-10 microns.
3. The nano composite auxiliary agent special for the casting linear low-density polyethylene anti-adhesive resin, as claimed in claim 1, is characterized in that the composite antioxidant is one or a mixture of more than two of phenolic antioxidants (1010, 1076, 300, 3114, etc.) and phosphite antioxidants (168, 626, etc.) in any proportion.
4. The nano composite additive special for the tape-casting linear low-density polyethylene anti-sticking resin is characterized in that the inorganic nano adsorption-nucleating agent is one or a mixture of more than two of organic modified nano silicon dioxide, organic modified nano titanium dioxide, organic modified nano zinc oxide, organic modified nano barium sulfate and organic modified nano calcium carbonate in any proportion.
5. The nano composite additive special for the tape-casting linear low-density polyethylene anti-sticking resin, as claimed in claim 1, is characterized in that the acid-absorbing stabilizer is one or a mixture of more than two of calcium stearate, zinc stearate, magnesium stearate and hydrotalcite in any proportion.
6. The nano composite additive special for the casting linear low-density polyethylene anti-sticking and slipping resin, as claimed in claim 1, is characterized in that the rheological additive is one or a mixture of more than two of ethylene bisstearamide and derivatives thereof, ethylene hydroxystearamide and derivatives thereof, stearic acid and alkali metal and alkaline earth metal salts thereof, hydroxystearic acid and alkali metal and alkaline earth metal salt thereof and fluorine-containing polymer PPA in any proportion.
7. The nano composite additive special for the casting linear low-density polyethylene anti-sticking and slipping resin as claimed in claim 1, wherein the yellow finger control agent is Na with a molecular formula of 6 Al 4 Si 6 S 4 O 20 One or two of nano inorganic ultramarine blue and ultramarine violet pigments in any proportion.
8. The preparation method of the nanocomposite auxiliary agent special for the casting linear low-density polyethylene anti-adhesive resin, as claimed in claim 1, is characterized by comprising the following steps:
1) Uniformly mixing the rheological additive, the anti-sticking agent, the inorganic nano adsorption-nucleating agent and the yellow index control agent by using a high-speed stirring device to perform;
2) Uniformly reinforcing the preformed component and other components into a composite material by adopting a gravity-free mixing device;
3) And curing the composite material at low temperature through parallel double screws, and finally obtaining the columnar composite additive with uniform size through a granule pressing forming and screening device.
9. The method for preparing the nano composite auxiliary agent special for the casting linear low-density polyethylene anti-adhesive resin, as claimed in claim 8, wherein the high-speed stirring device used in the process 1) is a double-screw high-speed stirring reaction device, and the process comprises the following steps of: the rotating speed is 100-130rpm, the temperature is controlled at 75-85 ℃, and the stirring time is 20-35min.
10. The method for preparing the nano composite auxiliary agent special for the casting linear low-density polyethylene anti-adhesive resin, as claimed in claim 8, wherein the gravity-free mixing device used in the process 2) is a double-shaft paddle mixer, the dust-free environment is regulated and controlled, and the process comprises the following steps: the rotating speed is 40-60rpm, the temperature is controlled at 75-85 ℃, and the stirring time is 30-40min.
11. The method for preparing the nano composite auxiliary agent special for the casting linear low-density polyethylene anti-adhesive resin, as claimed in claim 8, wherein the parallel double screw extruder is used in the process 3), and the process is as follows: the temperature is controlled to be 50-90 ℃, the rotating speed of a screw is controlled to be 0.2-0.45 ton/hour, the rotating speed of a granulator is controlled to be 0.2-0.45 ton/hour, the particle size of a screening device is controlled to be 2-4mm, and the particle size of the composite additive is controlled to be 5-7 g/particle.
12. The preparation method of the nano composite auxiliary agent special for the anti-adhesive resin of the casting linear low-density polyethylene according to the claims 9-11 is characterized in that the composite auxiliary agent is used for preparing the special material of the anti-adhesive casting linear low-density polyethylene, and the casting polyethylene film with excellent comprehensive properties such as good optics, mechanics, anti-adhesive, processing forming, thermal oxidative aging resistance and the like can be obtained. The nano composite auxiliary agent has the characteristics of integration, easy addition, small addition amount, low-temperature preparation and the like, and scientifically solves the difficulty of dust-free addition of the composite auxiliary agent in the production process of the special material of the tape-casting linear low-density polyethylene resin due to the accurate regulation and control of dust-free environment in the preparation process of the nano composite auxiliary agent.
CN202210643085.XA 2022-06-09 2022-06-09 Special nano composite auxiliary agent for tape-casting linear low-density polyethylene anti-adhesive resin and preparation method thereof Pending CN116162305A (en)

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CN112080042A (en) * 2019-06-12 2020-12-15 中国石油化工股份有限公司 Auxiliary agent composition and preparation method thereof, linear low-density polyethylene composition and preparation method thereof, and polyethylene casting packaging film

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CN112080042A (en) * 2019-06-12 2020-12-15 中国石油化工股份有限公司 Auxiliary agent composition and preparation method thereof, linear low-density polyethylene composition and preparation method thereof, and polyethylene casting packaging film

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