CN116790062A - High-melt-strength high-rigidity polypropylene composition and preparation method and application thereof - Google Patents
High-melt-strength high-rigidity polypropylene composition and preparation method and application thereof Download PDFInfo
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- -1 polypropylene Polymers 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 47
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000155 melt Substances 0.000 claims abstract description 57
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 39
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 27
- 229930195729 fatty acid Natural products 0.000 claims abstract description 27
- 239000000194 fatty acid Substances 0.000 claims abstract description 27
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 17
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 17
- 239000002667 nucleating agent Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920005633 polypropylene homopolymer resin Polymers 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000005022 packaging material Substances 0.000 claims description 2
- 238000000071 blow moulding Methods 0.000 abstract description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 17
- 229920003023 plastic Polymers 0.000 description 12
- 239000004033 plastic Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 238000000465 moulding Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 101000834948 Homo sapiens Tomoregulin-2 Proteins 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229920011250 Polypropylene Block Copolymer Polymers 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 102100026160 Tomoregulin-2 Human genes 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- FXDGCBFGSXNGQD-FAESFXMKSA-L disodium;(1s,2s,3r,4r)-bicyclo[2.2.1]heptane-2,3-dicarboxylate Chemical compound [Na+].[Na+].C1C[C@H]2[C@@H](C([O-])=O)[C@@H](C(=O)[O-])[C@@H]1C2 FXDGCBFGSXNGQD-FAESFXMKSA-L 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 239000002002 slurry Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 229940080350 sodium stearate Drugs 0.000 description 1
- CVYDEWKUJFCYJO-UHFFFAOYSA-M sodium;docosanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O CVYDEWKUJFCYJO-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
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Abstract
The application provides a high-melt-strength high-rigidity polypropylene composition, and a preparation method and application thereof. The polypropylene composition comprises the following components in parts by weight: 58-82 parts of homopolymerized polypropylene resin; 3-12 parts of long-chain branched low-density polyethylene resin; 15-30 parts of activated calcium carbonate; 0.1 to 0.4 part of nucleating agent; 0.1 to 0.3 part of processing aid; the melt index MFR of the long-chain branched low-density polyethylene resin is less than or equal to 0.75g/10min at 190 ℃/2.16 kg; the activated calcium carbonate is activated by long carbon chain fatty acid or fatty acid salt with carbon chain carbon number more than 12. According to the application, the melt strength and rigidity of the composition are improved by adding the long-branched low-density polyethylene resin, the long-carbon chain fatty acid activated calcium carbonate and the nucleating agent into the homo-polypropylene resin, and meanwhile, the ductility of the composition is not greatly influenced, so that the composition meets the requirements of a blow molding process.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a high-melt-strength high-rigidity polypropylene composition, and a preparation method and application thereof.
Background
Polypropylene is a very important general plastic, and has quite wide application and various processing modes, including injection molding, extrusion, blow molding, film blowing, plastic sucking and the like, wherein plastic sucking is a processing mode with wider application, and is widely applied to food packaging and the like, and the main requirements are that the melt strength and ductility of polypropylene and the rigidity at room temperature influence the application of a finished product.
The softening point and the melting point of polypropylene are very similar, so that the melt strength of general polypropylene is not too high, and the chemically synthesized high melt strength PP is not suitable for many application scenes because of quite high price. How to increase the melt strength of ordinary polypropylene has therefore also become a hot spot in the field of polypropylene research in recent years. Japanese patent JP55031807 discloses a method of preparing a foamed material by blending a polypropylene block copolymer with a polyethylene resin. The PP is blended with PMMA homopolymer or copolymer in US5506307 to obtain a modified material with better anti-sagging property, and the modified material can be used for producing articles such as vessels, cups and the like by thermoforming or extrusion molding. The patent CN101486817A is added with a compatilizer to prepare a PP/PA6 blending system, so that the melt strength and the comprehensive physical properties of the system are greatly improved. The patent CN103834102A prepares a material with excellent blow molding welding strength and comprehensive mechanical property by adding high-density polyethylene and SEPS into a polypropylene system, but the material mainly aims at meeting the requirements of a blow molding process. The patent CN112724508A greatly improves the melt strength of a system by adding a small amount of long-chain branched polypropylene into linear polypropylene, and further adds fluorine compounds into the system to form an interpenetrating network, so that the melt strength of the material is further improved, and the material meets the process requirements of blow molding or plastic suction.
However, the cost of polypropylene materials meeting the vacuum molding process is still too high in the prior art, and there is a need to develop a polypropylene composition which is easier to meet the vacuum molding process, and which has high melt strength and high rigidity.
Disclosure of Invention
The application provides a polypropylene composition which meets the requirements of a plastic sucking process and has high melt strength and high rigidity.
It is another object of the present application to provide a process for the preparation of said high melt strength high stiffness polypropylene composition.
It is a further object of the present application to provide the use of said high melt strength high stiffness polypropylene composition.
The above object of the present application is achieved by the following technical scheme:
the polypropylene composition comprises the following components in parts by weight:
58-82 parts of homopolymerized polypropylene resin;
3-12 parts of long-chain branched low-density polyethylene resin;
15-30 parts of activated calcium carbonate;
0.1 to 0.4 part of nucleating agent;
0.1 to 0.3 part of processing aid;
the melt index MFR of the long-chain branched low-density polyethylene resin is less than or equal to 0.75g/10min at 190 ℃/2.16 kg;
the activated calcium carbonate is activated by long carbon chain fatty acid or fatty acid salt with carbon chain carbon number more than 12.
The inventor finds that in the homopolymerized polypropylene resin, the melt strength of the material can be greatly improved by adding the long-chain branched low-density polyethylene resin, and the ductility of the composition is not influenced, so that the composition meets the requirement of a blow molding process. Meanwhile, the addition of the calcium carbonate activated by the long carbon chain fatty acid or fatty acid salt with carbon chain carbon number more than 12 can further improve the melt strength of the composition, the addition of the calcium carbonate has little influence on the ductility of the composition, and the calcium carbonate has a certain nucleation effect, but the nucleation effect can be further enhanced by matching with the nucleating agent, so that the rigidity of the composition at room temperature is further improved.
Further, the melt index of the homo-polypropylene resin is 1-12 g/10min at 230 ℃/2.16 kg.
Further, the melt index of the homo-polypropylene resin is 3-10 g/10min at 230 ℃/2.16 kg.
Further, the activated calcium carbonate is activated by long carbon chain fatty acid or fatty acid salt with carbon chain number of 12-22.
Further, the activated calcium carbonate is activated by long carbon chain fatty acid or fatty acid salt with 18-22 carbon chain carbon atoms.
The activation of calcium carbonate with fatty acids or fatty acid salts is a common method of activating calcium carbonate, typically during the preparation of calcium carbonate. Adding long-chain fatty acid or fatty acid salt into calcium carbonate slurry to form fatty acid calcium precipitate on the surface of calcium carbonate. Such activated calcium carbonate is commercially available directly.
Common long carbon chain fatty acids or fatty acid salts with carbon chain carbon number of 18-22 are, for example, oleic acid, sodium oleate, stearic acid, sodium stearate, behenic acid, sodium behenate and the like.
Further, the nucleating agent is one or more of carboxylate nucleating agent or phosphate nucleating agent.
Further, the melt index of the long-chain branched low-density polyethylene resin is 0.3-0.75 g/10min at 190 ℃/2.16 kg.
Further, the processing aid is an antioxidant.
Further, the antioxidant is selected from one or more of antioxidant 1010 (pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), antioxidant 168 (tris (2, 4-di-tert-butylphenyl) phosphite), antioxidant 1790 (1, 3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1 h,3h,5 h) -trione) or antioxidant 412S (pentaerythritol tetra-3-laurylthiopropionate).
In the present application, the melt index is tested according to the method specified in GB/T3682-2018 determination of melt Mass Flow Rate (MFR) and melt volume flow Rate (MVR) of plastics thermoplastics.
The preparation method of the high-melt-strength high-rigidity polypropylene composition comprises the following steps:
and (3) melting, blending, extruding and granulating the components by adopting a double-screw extruder, wherein the temperature of melting, blending is 180-220 ℃.
Further, the length-diameter ratio of the screws of the double-screw extruder is 44:1-52:1.
The application of the high-melt-strength high-rigidity polypropylene composition in preparing packaging materials.
Compared with the prior art, the application has the following beneficial effects:
the application discloses a high-melt-strength high-rigidity polypropylene composition, which is prepared by adding long-branched low-density polyethylene resin, long-carbon chain fatty acid activated calcium carbonate and a nucleating agent into homo-polypropylene resin, so that the melt strength and rigidity of the composition are improved, and meanwhile, the ductility of the composition is not greatly influenced, so that the composition meets the requirements of a blow molding process. Specifically, the melt strength of the polypropylene composition is more than 55mN, the melt stretching speed is more than 800mm/S, the bending modulus is more than 1600MPa, the sufficient melt strength can meet the capability of keeping the shape of the polypropylene composition in the plastic sucking process, the processing interval of the polypropylene composition can be larger, the melt stretching speed shows the ductility of the melt from the side, the sufficient ductility can ensure that the sheet material is not broken when in thermal deformation, the requirement of large deformation is met, the bending modulus is the rigidity of the polypropylene composition at the normal temperature, the sufficient bending modulus can enable the material to keep sufficient rigidity under the condition of being thinner after the material is deformed, and the performance of the polypropylene composition can enable the material to meet the application requirement when the plastic sucking deformation is larger. The composition has the advantages of easily obtained components, low price, lower cost than the existing composition of the same type, low requirement on production equipment and easy preparation.
Detailed Description
Technical solutions in the embodiments of the present application will be clearly and completely described below, but the embodiments of the present application are not limited thereto.
The reagents, methods and apparatus employed in the present application, unless otherwise specified, are all conventional reagents, methods and apparatus commercially available in the art.
The following examples and comparative examples were prepared from the following raw materials:
the homo-polypropylene resin HPP1 is purchased from China petrochemical industry Co., ltd, and has a melt index (230 ℃/2.16 kg) of 0.5g/10min;
the homo-polypropylene resin HPP2 is purchased from China petrochemical industry Co., ltd, and has a melt index (230 ℃/2.16 kg) of 3g/10min;
the homo-polypropylene resin HPP3 is purchased from China petrochemical industry Co., ltd, and has a melt index (230 ℃/2.16 kg) of 10g/10min;
the homo-polypropylene resin HPP4 is purchased from China petrochemical industry Co., ltd, and has a melt index (230 ℃/2.16 kg) of 30g/10min;
long-chain branched low density polyethylene PE1, available from China petrochemical Co., ltd, has a melt index (190 ℃/2.16 kg) of 0.3g/10min;
long-chain branched low density polyethylene PE2, available from China petrochemical Co., ltd, has a melt index (190 ℃/2.16 kg) of 0.75g/10min;
long-chain branched low density polyethylene PE3, available from China petrochemical Co., ltd, has a melt index (190 ℃/2.16 kg) of 4g/10min;
activated calcium carbonate CC1, purchased from england porcelain powder limited, activated with C12 fatty acid;
activated calcium carbonate CC2, purchased from england porcelain powder limited, activated with C18 fatty acid;
common calcium carbonate CC3, purchased from Cantonese Xianglong technologies Co., ltd, was not activated;
activated calcium carbonate CC4, available from Cantonese Xianglong technologies Inc., was activated with a silane coupling agent
Nucleating agent 1, carboxylate nucleating agent HPN-68L, available from Meldrum;
nucleating agent 2, phosphate nucleating agent NA-21, available from Ai Dike;
in the examples, the processing aid is antioxidant 1010 and antioxidant 168 in a ratio of 1:1 weight ratio of the mixed antioxidant compound. The antioxidants are all commercial products.
The preparation method comprises the following steps:
the materials are put into a high-speed mixer for mixing according to the formula of the table 1, and are melt-blended and extruded by a double-screw extruder with the length-diameter ratio of 48:1, and the temperature of a melting section is 180-220 ℃, so that the high-melt-strength high-rigidity polypropylene composition is obtained.
The materials were fed into a high speed mixer according to the formulation of Table 2, and melt blended and extruded through a twin screw extruder having an aspect ratio of 48:1, at a melting zone temperature of 180℃to 220℃to obtain the polypropylene composition of the comparative example.
Performance test of the composition:
test conditions for melt strength and melt tensile Rate at break: test temperature conditions: 200 ℃, screw rotation speed during test: 10rpm, using a melt tensile test module of a German Hak rheometer;
flexural modulus testing was performed according to national standard GB/T9341-2008.
Melt index MFR was measured according to the method specified in GB/T3682-2018 determination of melt Mass Flow Rate (MFR) and melt volume flow Rate (MVR) of plastics thermoplastics;
TABLE 1
TABLE 2
The results of the performance tests of the compositions of examples 1 to 9 and comparative examples 1 to 8 are shown in Table 3
TABLE 3 Table 3
From the data in Table 3, it is shown that the addition of the long-chain branched low-density polyethylene can effectively improve the melt strength of the composition, but the addition thereof can also have an effect on the melt fracture elongation rate, and from comparative example 7, the addition of too much of the long-chain branched low-density polyethylene can have a larger effect on the rigidity of the composition. As can be seen from a comparison of examples 2 and 7, the melt index of the long chain branched low density polyethylene is lower for the composition, which has a better effect on the improvement of the melt strength, the higher the melt index, the smaller the effect on the improvement of the melt strength, and the lower the rigidity of the composition. From comparative example 3, if the melt index of the long chain branched low density polyethylene is out of the range of the present application, it has insufficient improvement in melt strength and has a large influence on the rigidity of the composition.
Examples 6 and 7 show that the melt strength and the melt fracture stretching speed of the polypropylene resin matrix with different melt fingers are not consistent, the melt strength of the material prepared by the resin with lower melt fingers is better, but the melt fracture stretching speed is poorer, which indicates that the thermal deformation is poorer, holes are easy to generate in the plastic sucking processing, the melt strength of the material prepared by the resin with higher melt fingers is poorer, but the melt fracture stretching speed is higher, and the melt strength and the melt fracture stretching speed are both balanced only when the melt fingers are proper;
as can be seen from comparative examples 1 and 2, when the melt fingers of the polypropylene resin matrix are out of the scope of the present application, either insufficient melt stretch extension is caused for too low melt fingers or insufficient melt strength is caused for too high melt fingers to be easily sucked.
The carbon chain length of the fatty acid used for the activated calcium carbonate also has an effect on the change of the melt strength, and in the selected range, the longer the carbon chain, the more obvious the enhancement of the melt strength, and at the same time, the longer the carbon chain, the better the compatibility of the composition, so that the melt elongation at break of the composition prepared by the composition is better. The effect of carbon chain length on rigidity is not significant. From examples 7 and 8 and comparative example 6, if ordinary calcium carbonate which is not activated with fatty acid is used, it is insufficient in enhancement of melt strength and at the same time affects the melt stretching speed of the composition, i.e., the ductility of the composition is affected. In addition, from comparative example 8, if the silane coupling agent-activated calcium carbonate is used, the enhancement of the melt strength is still not significant, and the improvement of the melt stretching speed of the composition is insufficient.
Comparative example 5 reflects the effect of the additional addition of nucleating agent on the performance of the composition, and the rigidity of the composition is difficult to meet in the absence of the additional addition of nucleating agent.
The compositions of examples 1 to 9 and comparative examples 1 to 8 were formed into sheets having a thickness of 1mm, and then were vacuum molded into articles, and the articles were thinned after vacuum molding to give samples having a thickness of 0.2 to 0.4 mm. And visually observing the product after processing, the processing conditions are shown in Table 4:
TABLE 4 Table 4
As can be seen from table 4, when the melt strength of the composition was insufficient (< 55 mN), a poor suction molding easily occurred during the suction molding, resulting in molding problems; when the melt stretching rate is insufficient (< 800 mm/S), holes are easy to occur in the plastic sucking process, and insufficient bending modulus (< 1600 MPa) can lead to insufficient rigidity of the product after plastic sucking, so that the requirement of packaging with higher rigidity requirement can not be met.
It is to be understood that the above examples of the present application are provided by way of illustration only and not by way of limitation of the embodiments of the present application. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the application are desired to be protected by the following claims.
Claims (10)
1. The high-melt-strength high-rigidity polypropylene composition is characterized by comprising the following components in parts by weight:
the melt index MFR of the long-chain branched low-density polyethylene resin is less than or equal to 0.75g/10min at 190 ℃/2.16 kg;
the activated calcium carbonate is activated by long carbon chain fatty acid or fatty acid salt with carbon chain carbon number more than 12.
2. The high melt strength, high stiffness polypropylene composition according to claim 1, wherein the homo-polypropylene resin has a melt index of 1 to 12g/10min at 230 ℃/2.16 kg.
3. The high melt strength, high stiffness polypropylene composition according to claim 1, wherein the homo-polypropylene resin has a melt index of 3 to 10g/10min at 230 ℃/2.16 kg.
4. The high melt strength, high rigidity polypropylene composition according to claim 1 wherein the activated calcium carbonate is a calcium carbonate activated with a long carbon chain fatty acid or fatty acid salt having 12 to 22 carbon chain carbon atoms.
5. The high melt strength, high rigidity polypropylene composition according to claim 1 or 5 wherein the activated calcium carbonate is a calcium carbonate activated with a long carbon chain fatty acid or fatty acid salt having 18 to 22 carbon chain carbon atoms.
6. The high melt strength, high rigidity polypropylene composition according to claim 1, wherein the nucleating agent is one or more of carboxylate nucleating agent or phosphate nucleating agent.
7. The high melt strength, high stiffness polypropylene composition according to claim 1, wherein the long chain branched low density polyethylene resin has a melt index of from 0.3 to 0.75g/10min at 190 ℃/2.16 kg.
8. The method for producing a high melt strength, high rigidity polypropylene composition according to any one of claims 1 to 7, comprising the steps of:
and (3) melting, blending, extruding and granulating the components by adopting a double-screw extruder, wherein the temperature of melting, blending is 180-220 ℃.
9. The method of claim 8, wherein the twin screw extruder has a screw aspect ratio of 44:1 to 52:1.
10. Use of the high melt strength, high stiffness polypropylene composition according to any of claims 1 to 8 for the preparation of packaging materials.
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| CN202210266111.1A CN116790062A (en) | 2022-03-17 | 2022-03-17 | High-melt-strength high-rigidity polypropylene composition and preparation method and application thereof |
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| CN202210266111.1A CN116790062A (en) | 2022-03-17 | 2022-03-17 | High-melt-strength high-rigidity polypropylene composition and preparation method and application thereof |
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