CN117866292A - Special nano composite auxiliary agent for ethylene-propylene random copolymerization anti-sticking CPP resin and preparation method thereof - Google Patents
Special nano composite auxiliary agent for ethylene-propylene random copolymerization anti-sticking CPP resin and preparation method thereof Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 40
- 239000011347 resin Substances 0.000 title claims abstract description 40
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 21
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 18
- -1 polypropylene Polymers 0.000 claims abstract description 45
- 239000004743 Polypropylene Substances 0.000 claims abstract description 41
- 229920001155 polypropylene Polymers 0.000 claims abstract description 41
- 239000000654 additive Substances 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 230000000996 additive effect Effects 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 24
- 230000000181 anti-adherent effect Effects 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 230000003287 optical effect Effects 0.000 claims abstract description 10
- 238000012216 screening Methods 0.000 claims abstract description 10
- 238000010345 tape casting Methods 0.000 claims abstract description 8
- 239000002390 adhesive tape Substances 0.000 claims abstract description 7
- 230000033228 biological regulation Effects 0.000 claims abstract description 7
- 239000002667 nucleating agent Substances 0.000 claims abstract description 7
- 238000009775 high-speed stirring Methods 0.000 claims abstract description 5
- 238000010521 absorption reaction Methods 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000006254 rheological additive Substances 0.000 claims abstract description 4
- 239000003381 stabilizer Substances 0.000 claims abstract description 4
- 230000007613 environmental effect Effects 0.000 claims abstract description 3
- 239000008187 granular material Substances 0.000 claims abstract description 3
- 230000010354 integration Effects 0.000 claims abstract description 3
- 238000003825 pressing Methods 0.000 claims abstract description 3
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 3
- 238000005266 casting Methods 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- YQEDKRVSBHOVFJ-UHFFFAOYSA-N 1-(aziridin-1-yl)-2-hydroxyoctadecan-1-one Chemical compound OC(C(=O)N1CC1)CCCCCCCCCCCCCCCC YQEDKRVSBHOVFJ-UHFFFAOYSA-N 0.000 claims description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 claims description 2
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- HNMCSUXJLGGQFO-UHFFFAOYSA-N hexaaluminum;hexasodium;tetrathietane;hexasilicate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].S1SSS1.S1SSS1.[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] HNMCSUXJLGGQFO-UHFFFAOYSA-N 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 235000013799 ultramarine blue Nutrition 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 238000010899 nucleation Methods 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000003712 anti-aging effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 11
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a special nano composite additive for ethylene-propylene random copolymerization anti-adhesive tape casting polypropylene (CPP) resin and a preparation method thereof, comprising the following steps: 20% -30% of an anti-adhesion agent, 20% -30% of an antioxidant, 20% -30% of an inorganic nano adsorption-nucleating agent, 5% -15% of an acid absorption stabilizer, 10% -15% of a rheological additive and 0.01% -0.1% of a yellow finger control agent. The preparation technology comprises the following steps: 1) Uniformly mixing the anti-sticking agent, the inorganic nano adsorption-nucleating agent, the rheological auxiliary 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 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 CPP resin to obtain ideal optical, mechanical, anti-adhesion, anti-aging, heat-resistant and other excellent comprehensive properties and easy-to-process molding processes, and in addition, the auxiliary agent has the product characteristics of integration, small addition amount, low-temperature process, environmental protection and the like, and the preparation process can realize the accurate regulation and control of dust-free environment and the dust-free addition of the auxiliary agent in the resin production process.
Description
Technical Field
The invention relates to a special nano composite additive for ethylene-propylene random copolymerization anti-adhesive tape casting polypropylene (CPP) resin, belonging to the field of multifunctional composite additives for polymers.
Background
The polypropylene 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 polypropylene packaging film is particularly suitable for the packaging fields with high requirements on heat sealing and optical performance of packaging materials, such as foods, medicines, clothing, flowers, daily chemicals and the like.
The three-layer coextrusion casting is a main production process of the domestic outer casting polypropylene film, and the three-layer coextrusion casting 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, so that the film is endowed with different performances and purposes.
The corona layer accounts for 15-25% of the total film weight, and is a functional layer which is subjected to printing, compounding or metallization treatment after corona treatment. The corona layer requires strong corona value retention, proper tension, good stiffness, glossiness and anti-blocking property, and strictly controls low molecular component, low molecular content and migration degree to directly influence corona efficiency and firm strength of compounding, printing and metallization. Ethylene-propylene random copolymer casting polypropylene (CPP) resin with single anti-adhesive function is a common resin.
The core layer accounts for 50-70% of the total film weight, is a mechanical support of the three-layer film, has a certain influence on the film optical property, and is required to have good rigidity, stiffness and optical properties (low haze and high glossiness) and simultaneously can reduce the cost. The core layer resin is mainly made of homopolymerized polypropylene (PPH) with lower cost, but the film material with higher performance requirements, such as a steamed film, is generally made of ethylene-propylene random copolymer casting polypropylene (CPP) special material with better impact strength.
At present, the special material for the ethylene-propylene random copolymerization anti-sticking casting polypropylene mainly has the following problems: the appearance of the film is easy to generate crystal points, the section is yellow or red, the transparency and glossiness are poor, the film is easy to adhere and difficult to open in a casting (non-inflation) process, the impact toughness is insufficient, the heat resistance is poor, the heat sealing temperature is high, and the like, and the problems can be solved by optimizing the physical properties of the base materials through the polymer production process of petrochemical enterprises, but the method is limited by devices and technologies, the regulation and control range is limited and the cost is high, so that the method is a general polymer modification method which is convenient to operate, has proper cost and wider adjustable range and is added with a multifunctional integrated composite auxiliary agent for blending modification in the granulation stage.
In recent years, the nano material 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, quantum size effect and the like, namely, the nano functional auxiliary agent and the processing auxiliary agent are compounded and added in a small amount in the granulating stage of the special material for the ethylene-propylene random copolymer casting polypropylene, so that the problem of the special material for the ethylene-propylene random copolymer anti-sticking casting polypropylene at present is effectively solved.
Disclosure of Invention
The invention aims to provide a nano composite additive special for ethylene-propylene random copolymerization anti-adhesive casting polypropylene (CPP) resin and a preparation method thereof aiming at the technical problems. The nano composite additive has the characteristics of integration, easy addition, small addition amount, low-temperature preparation, environmental protection 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 additive and dust-free addition of the composite additive in the production process of the special polypropylene resin material. The film prepared by casting the special material of the ethylene-propylene PPR anti-adhesive casting resin added with the composite additive has good comprehensive properties (corona layer, core layer) of optics, mechanics, anti-adhesive, processing and forming, thermal-oxidative aging resistance and the like.
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:
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 composite antioxidant is one or a mixture of more than two of phenolic antioxidants (1010, 1076, 330, 300, 3114, etc.) and phosphite antioxidants (168, 626, etc.).
The inorganic nano 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 special nano composite additive for ethylene-propylene random copolymerization anti-adhesive tape casting polypropylene (CPP) resin, which comprises the following steps:
1) The anti-sticking agent, the inorganic nano nucleating agent, the rheological additive 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 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 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.
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
As is clear from Table 2, the impact strength of the polypropylene product added with the product is obviously increased, and the strength, toughness and temperature resistance of the polypropylene product are improved to a great extent.
The technical scheme provided by the invention has the beneficial effects that:
the binary ethylene-propylene random copolymer casting polypropylene resin is taken as a base material, and an integrated functional nano composite auxiliary agent is adopted to comprehensively improve the optical, mechanical, anti-adhesion, processing and molding performances, thermo-oxidative aging resistance and other performances of the film product, solve the difficulty of adding the auxiliary agent in the production process of the random copolymer casting polypropylene resin, and simultaneously remarkably improve the comprehensive performance of the casting polypropylene film:
(1) Optical, anti-sticking, processing rheology synergy: the complex application of the inorganic nano 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 phenomenon of shark slices 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 residues in the production process of the special resin for the cast polypropylene, and selecting modified inorganic nano materials with higher temperature resistance for targeted adsorption according to the production process method of the resin and the production characteristics of the cast 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 schematic illustration of the process flow.
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 formula for the ethylene-propylene binary random copolymerization anti-adhesive tape casting polypropylene special resin and the preparation method thereof comprise the following components in percentage by mass: 20% of an antioxidant (168), 10% of an antioxidant (1010), 3% of a dispersing agent, 10% of a heat stabilizer, 2% of an antistatic agent, 1.5% of an ultraviolet-resistant absorbent, 10% of an adhesive, 20% 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 PPH-T03, and a heat sealing layer is 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 formula for the ethylene-propylene binary random copolymerization anti-adhesive tape casting polypropylene special resin and the preparation method thereof comprise 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, 2% of an ultraviolet-resistant absorbent, 15% of an adhesive, 30% of inorganic nano functional particle barium sulfate and 0.07% 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 formula for the ethylene-propylene binary random copolymerization anti-adhesive tape casting polypropylene special resin and the preparation method thereof comprise the following components in percentage by mass: 15% of antioxidant (168), 15% of antioxidant (1010), 4% of dispersing agent, 5% of heat stabilizer, 3% of antistatic agent, 1% of ultraviolet-resistant absorbent, 10% of adhesive, 15% of inorganic nano functional particle calcium carbonate, 15% of inorganic nano functional particle barium sulfate and 0.09% of yellowing resistant 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
| Project | Example 1 | Example 2 | Example 3 | Atactic polypropylene resin |
| Solution flow Rate, g/10min | 6.56 | 6.85 | 7.12 | 4.86 |
| Film thickness, μm | 40 | 40 | 40 | 40 |
| Transmittance of light,% | 92.15 | 91.78 | 92.37 | 90.21 |
| Haze (%) | 4.7 | 5.2 | 0.97 | 5 |
| Gloss [ ]Gs，20°) | 86.7 | 88.9 | 93.6 | 75.6 |
| Tensile strength [ ]MPa) | 20.87 | 22.65 | 28.09 | 19.21 |
| Elongation at break (%) | 1067.17 | 1190.08 | 1322.67 | 988.35 |
| Simply supported impact Strength | 12.30 | 12.07 | 17.78 | 3.08 |
| Heat distortion temperature (DEG C) | 82 | 85 | 94 | 67 |
| Yellow index after irradiation (40 KGy) | -1 | -0.56 | -2 | 20 |
As shown by the test result data in the table 3, the composite additive obviously improves the mechanical property, the heat distortion temperature, the yellow index after radiation (40 KGy) and the processability of the ethylene-propylene random copolymer polypropylene resin, and obviously 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 (13)
1. The nanometer composite auxiliary agent special for the ethylene-propylene random copolymerization anti-adhesive tape casting polypropylene (CPP) resin is mainly characterized by comprising the following formula components in percentage by mass:
20% -30% of anti-adhesion agent
20-30% of composite antioxidant
20-30% of inorganic nano adsorption-nucleating agent
5 to 15 percent of acid absorption stabilizer
10 to 15 percent of rheological additive
The yellow index control agent accounts for 0.01 to 0.1 percent.
2. The nano composite additive special for ethylene-propylene random copolymerization anti-adhesive casting polypropylene (CPP) resin, as claimed in claim 1, is characterized in that the anti-adhesive 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 additive special for ethylene-propylene random copolymerization anti-adhesive casting polypropylene (CPP) resin as claimed in claim 1, wherein the composite antioxidant is one or a mixture of more than two of phenolic antioxidants (1010, 1076, 330, 300, 3114, etc.) and phosphite antioxidants (168, 626, etc.) in any proportion.
4. The nanocomposite aid special for ethylene-propylene random copolymerization anti-adhesive casting polypropylene (CPP) resin, as claimed in claim 1, is characterized in that the inorganic nano adsorption-nucleation 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 ethylene-propylene random copolymerization anti-adhesive casting polypropylene (CPP) resin, as claimed in claim 1, is characterized in that the acid absorption 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 ethylene-propylene random copolymerization anti-adhesive casting polypropylene (CPP) resin as claimed in claim 1, wherein 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 salts thereof, and fluorine-containing polymer PPA in any proportion.
7. The nanometer composite additive special for ethylene-propylene random copolymer anti-sticking and anti-stretching polypropylene (CPP) resin as set forth in claim 1, wherein 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.
8. The preparation method of the nanocomposite aid special for the ethylene-propylene random copolymerization anti-adhesive casting polypropylene (CPP) resin, which is disclosed in claim 1, is characterized by comprising the following steps:
1) Uniformly mixing the anti-sticking agent, the inorganic nano adsorption-nucleating agent, the rheological auxiliary 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 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 preparation method of the nano composite additive special for the ethylene-propylene random copolymerization anti-adhesive casting polypropylene (CPP) resin, which is characterized in that the high-speed stirring device used in the process 1) is a double-screw high-speed stirring reaction device, dust-free environment regulation and control are carried out, and 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.
10. The method for preparing the special nano composite additive for the ethylene-propylene random copolymerization anti-adhesive casting polypropylene (CPP) resin, which is characterized in that a 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 nanocomposite auxiliary agent special for ethylene-propylene random copolymerization anti-adhesive casting polypropylene (CPP) resin, as claimed in claim 9, wherein in the process 3), a parallel double-screw extruder is used, and 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 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 special nano composite additive for the ethylene-propylene random copolymerization anti-adhesive casting polypropylene (CPP) resin, which is disclosed in the claims 10-12, is characterized in that the nano composite additive has the characteristics of integration, easy addition, small addition amount, low-temperature preparation, environmental protection 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 additive and dust-free addition of the composite additive in the production process of special polypropylene resin materials.
13. In addition, the ethylene-propylene CPP resin special material added with the auxiliary agent has good optical, heat-resistant, mechanical, ultraviolet aging resistant, anti-sticking, anti-impact and excellent processing and forming properties.
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