CN105623103A - Impact-resistant polypropylene material with high melt strength - Google Patents
Impact-resistant polypropylene material with high melt strength Download PDFInfo
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- CN105623103A CN105623103A CN201410602224.XA CN201410602224A CN105623103A CN 105623103 A CN105623103 A CN 105623103A CN 201410602224 A CN201410602224 A CN 201410602224A CN 105623103 A CN105623103 A CN 105623103A
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- -1 polypropylene Polymers 0.000 title claims abstract description 168
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 156
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 156
- 239000000463 material Substances 0.000 title claims abstract description 75
- 229920005653 propylene-ethylene copolymer Polymers 0.000 claims abstract description 17
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims abstract description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008096 xylene Substances 0.000 claims abstract description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 34
- 239000005977 Ethylene Substances 0.000 claims description 34
- 229920005604 random copolymer Polymers 0.000 claims description 33
- 239000000155 melt Substances 0.000 claims description 25
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 21
- 238000009826 distribution Methods 0.000 claims description 20
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 20
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 12
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 4
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- 238000007789 sealing Methods 0.000 abstract description 4
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- 238000004566 IR spectroscopy Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 125000000217 alkyl group Chemical group 0.000 description 3
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 3
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- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
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- NGMVWDKVVMVTTM-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-3-methylbutane Chemical compound COCC(C(C)C)COC NGMVWDKVVMVTTM-UHFFFAOYSA-N 0.000 description 1
- QQQXNLBGXGXTHL-UHFFFAOYSA-N 2,4-diethoxybutylcyclohexane Chemical compound C1(CCCCC1)CC(CCOCC)OCC QQQXNLBGXGXTHL-UHFFFAOYSA-N 0.000 description 1
- JUJMPCLNRKYKRA-UHFFFAOYSA-N 2,4-dimethoxybutylcyclohexane Chemical compound COCCC(OC)CC1CCCCC1 JUJMPCLNRKYKRA-UHFFFAOYSA-N 0.000 description 1
- HBHVBOUUMCIGMG-UHFFFAOYSA-N 2,6-Dibutyl-p-cresol Natural products CCCCC1=CC(O)=CC(CCCC)=C1O HBHVBOUUMCIGMG-UHFFFAOYSA-N 0.000 description 1
- LZFZQYNTEZSWCP-UHFFFAOYSA-N 2,6-dibutyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC(CCCC)=C1O LZFZQYNTEZSWCP-UHFFFAOYSA-N 0.000 description 1
- DBCCDXWGWMPKBB-UHFFFAOYSA-N 2,6-dimethyl-3,3-bis(propoxymethyl)heptane Chemical compound C(C)(C)C(COCCC)(COCCC)CCC(C)C DBCCDXWGWMPKBB-UHFFFAOYSA-N 0.000 description 1
- HEUKEUVOQISEPV-UHFFFAOYSA-N 3,3-bis(ethoxymethyl)-2,6-dimethylheptane Chemical compound CCOCC(CCC(C)C)(COCC)C(C)C HEUKEUVOQISEPV-UHFFFAOYSA-N 0.000 description 1
- BHPDSAAGSUWVMP-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(C(C)C)(COC)CCC(C)C BHPDSAAGSUWVMP-UHFFFAOYSA-N 0.000 description 1
- PVWCLOAAEFMTLH-UHFFFAOYSA-N 4,4-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(COC)(CC(C)C)CC(C)C PVWCLOAAEFMTLH-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
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- 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 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- HLXKHZZBHUAIQI-UHFFFAOYSA-N [2,2-bis(methoxymethyl)-3-methylbutyl]cyclohexane Chemical compound COCC(COC)(C(C)C)CC1CCCCC1 HLXKHZZBHUAIQI-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GVVHLVYPTGVRPW-UHFFFAOYSA-N [3-methoxy-2-(methoxymethyl)propyl]benzene Chemical compound C(C1=CC=CC=C1)C(COC)COC GVVHLVYPTGVRPW-UHFFFAOYSA-N 0.000 description 1
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
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- JOUWRCGZMOSOCD-UHFFFAOYSA-N cyclopentyl-dimethoxy-propan-2-ylsilane Chemical compound CO[Si](OC)(C(C)C)C1CCCC1 JOUWRCGZMOSOCD-UHFFFAOYSA-N 0.000 description 1
- XFAOZKNGVLIXLC-UHFFFAOYSA-N dimethoxy-(2-methylpropyl)-propan-2-ylsilane Chemical compound CO[Si](C(C)C)(OC)CC(C)C XFAOZKNGVLIXLC-UHFFFAOYSA-N 0.000 description 1
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- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
- BJDLPDPRMYAOCM-UHFFFAOYSA-N triethoxy(propan-2-yl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)C BJDLPDPRMYAOCM-UHFFFAOYSA-N 0.000 description 1
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- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides an impact-resistant polypropylene material with high melt strength. The polypropylene material comprises a random-copolymerized polypropylene continuous phase and a propylene-ethylene copolymer rubber dispersion phase; the content of xylene soluble matter in the material at room temperature is higher than or equal to 10wt% and is lower than or equal to 35wt%; and the ratio of the Mw of trichlorobenzene soluble matter at room temperature to the Mw of trichlorobenzene insoluble matter at room temperature is greater than 0.4 and is smaller than or equal to 1. The polypropylene material provided by the invention has high melt strength, also has the characteristics of high rigidity, high toughness and easiness in heat sealing and is extensive in application, for example, is applicable to the fields of automotive parts, medical appliances, household items and the like.
Description
Technical Field
The invention relates to a polypropylene material, in particular to an impact-resistant polypropylene material with high melt strength and a preparation method thereof.
Background
The impact-resistant polypropylene has excellent high and low temperature impact strength, higher rigidity such as tensile strength, flexural modulus and the like and higher heat resistance temperature, and is widely applied to various fields such as molded or extruded automobile parts, household appliance parts, containers, household goods and the like. The impact polypropylene is generally used for injection processing due to low melt strength, and when the impact polypropylene is used for blow molding, the problems of unstable size of a mold blank, uneven thickness of a product and even no molding can be realized, and the like exist.
A common practice to increase the melt strength of polypropylene is to lower the melt index, i.e. increase the polypropylene molecular weight, but this can lead to difficulties in melting and extruding the material. Another method is to broaden the molecular weight distribution, for example, US7365136 and US6875826 report a method for preparing homo-and random-copolymerized polypropylene with wide molecular weight distribution and high melt strength, which selects alkoxysilane as an external electron donor (such as dicyclopentyldimethoxysilane), and regulates the molecular weight and distribution by adjusting the hydrogen concentration in a plurality of reactors connected in series, thereby achieving the effect of improving the melt strength of polypropylene. WO9426794 discloses a process for the preparation of high melt strength homo-and random co-polypropylene in multiple reactors in series by adjusting the hydrogen concentration in the different reactors to prepare high melt strength polypropylene with broad molecular weight distribution or bimodal distribution, the properties of the catalyst being not adjusted in the individual reactors, so that a large amount of hydrogen is required for the preparation process.
CN102134290 and CN102134291 disclose a preparation method of homo-polypropylene with wide molecular weight distribution and high melt strength, which adopts a plurality of reactors connected in series to prepare homo-polypropylene or random co-polypropylene with wide molecular weight distribution and high melt strength by controlling the types and proportions of external electron donor components in different reaction stages and combining the control of hydrogen dosage of a molecular weight regulator.
The chinese application patent 201210422726.5 also reports a preparation method for obtaining homo-polypropylene or random co-polypropylene with wide molecular weight distribution and high melt strength by adjusting and controlling the isotactic index and hydrogen regulation sensitivity of the catalyst in different reactors through the reasonable matching of two different types of external electron donors, namely silane and diether.
The above patents report methods for preparing homo-polypropylene or random co-polypropylene having high melt strength, that is, homo-polypropylene or random co-polypropylene prepared by these methods have insufficient rigidity, toughness or impact resistance in spite of having high melt strength, thereby limiting the applications of the obtained polypropylene. Therefore, it would be of great significance to provide an impact polypropylene having high melt strength, high rigidity and toughness with a rubber component and a dispersed phase structure of rubber, and a method for preparing the same.
Disclosure of Invention
The inventor of the invention provides a high-melt-strength impact-resistant polypropylene material through intensive research, and the polypropylene material also has the characteristics of high toughness and easiness in heat sealing. The polypropylene material is an excellent material suitable for the fields of automobile parts, medical instruments, household articles and the like.
The invention also provides a method for preparing the impact-resistant polypropylene material with high melt strength. The polypropylene material obtained by the method of the invention also has the characteristic of high toughness.
According to the present invention, there is provided a high melt strength impact polypropylene material comprising a random copolymerized polypropylene continuous phase and a propylene-ethylene copolymer rubber dispersed phase, wherein the random copolymerized polypropylene continuous phase comprises at least a first random copolymerized polypropylene and a second random copolymerized polypropylene, and the first random copolymerized polypropylene and the second random copolymerized polypropylene are each independently selected from a propylene-ethylene random copolymer or a propylene-1-butene random copolymer or an ethylene-propylene-1-butene terpolymer; the material has a room temperature xylene solubles content of greater than or equal to 10 wt% and less than or equal to 35 wt%; and the ratio of the Mw (weight average molecular weight) of the room temperature trichlorobenzene soluble matter of the material to the Mw of the room temperature trichlorobenzene insoluble matter is more than 0.4, less than or equal to 1, such as more than 0.4 and less than or equal to 0.8. The polypropylene material has excellent rigidity and toughness and higher melt strength.
In the present invention, the content of the rubber phase, as the xylene soluble content at room temperature, can be determined according to the CRYSTEX method. For ease of characterization, the molecular weight of the rubber phase is based on the molecular weight of the trichlorobenzene solubles.
In the polypropylene material provided by the invention, the random copolymerization polypropylene is used as a continuous phase to provide certain rigidity for the polypropylene material, and the propylene-ethylene copolymer rubber is used as a disperse phase to improve the toughness of the polypropylene material. In order to ensure that the product of the invention has better rigidity-toughness balance, the invention adopts ethylene-propylene copolymer as the rubber component, and the inventor of the invention finds that in the impact polypropylene material of the invention, when the ethylene content in the xylene soluble at room temperature of the material is more than or equal to 28 weight percent and less than 45 weight percent, the impact polypropylene material has better rigidity and toughness. In particular, in the present invention, by arranging the random copolymer polypropylene continuous phase to include at least a first random copolymer polypropylene and a second random copolymer polypropylene, and the first random copolymer polypropylene and the second random copolymer polypropylene are each independently selected from a propylene-ethylene random copolymer or a propylene-1-butene random copolymer or an ethylene-propylene-1-butene terpolymer, the continuous phase and the dispersed phase are better compounded with each other, resulting in an impact polypropylene material with high melt strength and high toughness. It is to be understood that the term "ethylene content" as used herein means the weight content of the portion of ethylene monomer in the polymer in which the ethylene monomer is present. The other stands for "butene content" in the polymer, which is synonymous therewith.
In order to obtain higher melt strength, the melt index of the impact polypropylene material of the present invention is preferably controlled in the range of 0.1 to 15g/10min, and more preferably 0.1 to 6.0g/10 min. The melt index was measured at 230 ℃ under a load of 2.16 kg. For high melt strength impact polypropylene, the factors affecting melt strength become more complex due to the material being of multi-phase structure. The inventors have found that, in order to ensure a high melt strength of the product, the impact polypropylene material preferably has a molecular weight distribution Mw/Mn (weight average molecular weight/number average molecular weight) of less than or equal to 10 and greater than or equal to 4, for example 4, 5, 6, 7, 8, 9 or 10; mz +1/Mw is preferably greater than or equal to 10 and preferably less than 20.
In some preferred embodiments, the impact polypropylene material of the present invention has an ethylene content of from 8 to 20 weight percent; and/or a butene content of 0 to 10% by weight.
The impact polypropylene material according to the present invention has a molecular weight Polydispersity Index (PI) of from 4 to 10, preferably from 4.5 to 6.
In a preferred embodiment of the present invention, the first random copolymer polypropylene has a melt index smaller than that of the second random copolymer polypropylene.
In a preferred embodiment of the present invention, the first random copolymer polypropylene has a melt index of 0.001 to 0.4g/10min measured at 230 ℃ under a load of 2.16 kg; the random copolymer polypropylene comprising the first random copolymer polypropylene has a melt index of 0.1 to 15g/10min as measured at 230 ℃ under a load of 2.16 kg. Preferably 0.1-6g/10 min.
Preferably, the weight ratio of the first random copolymerized polypropylene and the second random copolymerized polypropylene is 40:60 to 60: 40. By arranging the random copolymerized polypropylene continuous phase of the impact polypropylene material of the present invention to include a combination of at least two random copolymerized polypropylenes having different melt indexes and having a specific proportional relationship, the polypropylene material constituting the present invention is provided with a specific continuous phase, particularly under the condition that the first random copolymerized polypropylene and the random copolymerized polypropylene including the first random copolymerized polypropylene and the second random copolymerized polypropylene respectively have specific different molecular weights and molecular weight distributions, and further combination of the continuous phase and a specific dispersed phase, i.e., rubber phase, results in an impact polypropylene material having both high melt strength and good rigidity and toughness.
According to a preferred embodiment of the present invention, the random copolymer polypropylene continuous phase constituting the impact polypropylene material of the present invention has the following characteristics:
a melt index, measured at 230 ℃ under a load of 2.16kg, of 0.1 to 10g/10min, preferably 0.1 to 6g/10 min;
molecular weight distribution Mw/Mn is 6-20, preferably Mw/Mn is 10-16;
the fraction having a molecular weight of more than 500 ten thousand is present in an amount of more than or equal to 1.5% by weight and less than or equal to 5% by weight;
the content of fractions having a molecular weight of less than 5 ten thousand is greater than or equal to 15.0% by weight and less than or equal to 40% by weight;
mz +1/Mn is greater than or equal to 70 and preferably less than 150.
According to the invention, the content of ethylene in the random copolymerization polypropylene continuous phase is preferably 0-6 wt%; and/or the butene content is 0 to 10% by weight.
According to the present invention, there is provided an impact polypropylene material prepared by subjecting a propylene-based random copolymerization reaction in the presence of a first random copolymerized polypropylene to obtain a random copolymerized polypropylene continuous phase comprising the first random copolymerized polypropylene and a second random copolymerized polypropylene, and then subjecting a propylene-ethylene copolymerization reaction in the presence of the random copolymerized polypropylene continuous phase to obtain a material comprising a propylene-ethylene copolymer rubber phase. It can be seen that the impact polypropylene material of the present invention is not simply a mixture of a random copolymerized polypropylene continuous phase and a propylene-ethylene copolymer rubber dispersed phase, but is an integral polypropylene material comprising a random copolymerized polypropylene continuous phase and a propylene-ethylene copolymer rubber dispersed phase obtained after further performing propylene-ethylene copolymerization on the basis of the random copolymerized polypropylene continuous phase.
According to a preferred embodiment of the present invention, the ratio of the melt index of the random copolymerized polypropylene continuous phase to the melt index of the polypropylene material comprising the random copolymerized polypropylene continuous phase and the propylene-ethylene copolymer rubber dispersed phase obtained in the second step is greater than or equal to 0.6 and less than 1.
According to a preferred embodiment of the present invention, the weight ratio of the propylene-ethylene copolymer rubber dispersed phase to the random copolymerized polypropylene continuous phase is 11 to 80: 100.
The polypropylene material also has better heat resistance and better heat sealing performance, and the melting peak temperature T of the final polypropylene resin is measured by DSCm145 ℃ or higher and 158 ℃ or lower.
According to the present invention, there is also provided a process for preparing a high melt strength impact polypropylene material as described above, comprising:
the first step is as follows: random copolymerization of propylene groups comprising:
the first stage is as follows: carrying out random copolymerization of propylene and ethylene and/or 1-butene in the presence or absence of hydrogen under the action of a Ziegler-Natta catalyst containing a first external electron donor to obtain a reaction stream containing first random copolymerized polypropylene;
and a second stage: adding a second external electron donor to perform a complex reaction with a catalyst in the reactant flow, and then performing a random copolymerization reaction of propylene and ethylene and/or 1-butene in the presence of the first random copolymerization polypropylene and hydrogen to generate second random copolymerization polypropylene, so as to obtain a random copolymerization polypropylene continuous phase containing the first random copolymerization polypropylene and the second random copolymerization polypropylene;
wherein,
the first random copolymerized polypropylene and the random copolymerized polypropylene continuous phase containing the first random copolymerized polypropylene and the second random copolymerized polypropylene respectively have melt indexes of 0.001-0.4g/10min and 0.1-15g/10min at 230 ℃ and under the load of 2.16 kg;
the second step is that: and (3) propylene-ethylene copolymerization, namely performing propylene-ethylene gas phase copolymerization in the presence of the random copolymerization polypropylene continuous phase and hydrogen to generate a propylene-ethylene copolymer rubber dispersed phase, so as to obtain the material containing the random copolymerization polypropylene continuous phase and the propylene-ethylene copolymer rubber dispersed phase.
In the first stage, the amount of hydrogen used may be, for example, from 0 to 200 ppm. In the second stage, the amount of hydrogen used was 2000-. The process provided by the present invention is preferably carried out in two or more reactors operated in series.
The process according to the invention is a Ziegler-Natta catalyst direct catalysed polymerisation process. The method comprises the steps of respectively using two or more different types of external electron donors in a plurality of reactors connected in series, selecting a proper amount of the external electron donors, combining different amounts of chain transfer agent hydrogen, reaction monomer compositions and the like in the reaction to prepare a random copolymerization polypropylene continuous phase with a specific melt index and a large amount of ultrahigh molecular weight components and extremely wide molecular weight distribution, further carrying out copolymerization of propylene and ethylene on the basis to obtain a rubber phase dispersed in the continuous phase, and controlling the composition, structure, content and the like of the rubber phase by controlling the reaction conditions of the copolymerization reaction to obtain the impact-resistant polypropylene material with a high melt strength effect.
In the process provided by the present invention, the catalyst used is a Ziegler-Natta catalyst, preferably a catalyst with high stereoselectivity. The Ziegler-Natta catalyst having high stereoselectivity as used herein means a catalyst which can be used for the preparation of a propylene homopolymer having an isotactic index of more than 95%. Such catalysts generally comprise (1) a titanium-containing solid catalyst active component, the main components of which are magnesium, titanium, halogen and an internal electron donor; (2) an organoaluminum compound co-catalyst component; (3) an external electron donor component.
The solid catalyst active component (which may also be referred to as a procatalyst) of the Ziegler-Natta catalyst used in the process of the present invention may be well known in the art. Specific examples of such active solid catalyst component (1) containing that can be used are, for example, described in patent documents CN85100997, CN98126383.6, CN98111780.5, CN98126385.2, CN93102795.0, CN00109216.2, CN99125566.6, CN99125567.4 and CN 02100900.7. These patent documents are incorporated by reference herein in their entirety.
The organoaluminum compound in the Ziegler-Natta catalyst used in the process of the present invention is preferably an alkylaluminum compound, more preferably a trialkylaluminum, for example, at least one of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, trihexylaluminum and the like.
The molar ratio of the titanium-containing active solid catalyst component and the organoaluminum compound in the Ziegler-Natta catalyst used in the process of the present invention is 10:1 to 500:1, preferably 25:1 to 100:1, in terms of aluminum/titanium.
According to the invention, said first external electron donor is preferably selected from those of formula R1R2Si(OR3)2At least one of the compounds of (a); wherein R is2And R1Each independently selected from C1-C6Straight or branched alkyl, C3-C8Cycloalkyl and C5-C12Heteroaryl of (A), R3Is C1-C3A straight chain aliphatic group. Specific examples include, but are not limited to, dicyclopentyldimethoxysilane, isopropylcyclopentyldimethoxysilane, isopropylisobutyldimethoxysilane, dipyridyldimethoxysilane, diisopropyldimethoxysilane, and the like.
The molar ratio of the organic aluminum compound to the first external electron donor is 1:1 to 100:1, preferably 10:1 to 60:1, calculated as aluminum/silicon.
In the process according to the invention, the catalyst comprising the first external electron donor may be fed directly to the first random copolymerization reactor or may be fed to the first random copolymerization reactor after pre-contacting and/or pre-polymerization as known in the art. The prepolymerization refers to that the catalyst is prepolymerized at a certain ratio at a lower temperature to obtain the ideal particle shape and dynamic behavior control. The prepolymerization can be liquid phase bulk continuous prepolymerization, and can also be batch prepolymerization in the presence of an inert solvent. The temperature of the prepolymerization is usually-10 to 50 ℃ and preferably 5 to 30 ℃. A precontacting step may optionally be provided before the prepolymerization process. The pre-contact step refers to the complex reaction of a cocatalyst, an external electron donor and a main catalyst (solid active center component) in the catalyst system to obtain the catalyst system with polymerization activity. The temperature in the precontacting step is usually controlled to be-10 to 50 ℃, preferably 5 to 30 ℃.
According to the invention, the second external electron donor is selected from at least one of the compounds shown in the chemical general formulas (I), (II) and (III);
wherein R is1And R2Each independently selected from C1-C20Straight-chain, branched or cyclicOne of the aliphatic radicals, R3、R4、R5、R6、R7And R8Each independently selected from a hydrogen atom, a halogen atom, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl and C7-C20One of aralkyl, and R3、R4、R5、R6、R7And R8Optionally linked to form a ring between any two of them; r9、R10And R11Each independently is C1-C3Straight-chain aliphatic radical, R12Is C1-C6Straight or branched alkyl or C3-C8A cycloalkyl group. Specific examples of the second external electron donor include, but are not limited to, 2-diisobutyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2-benzyl-1, 3-dimethoxypropane, 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isopropyl-2-3, 7-dimethyloctyl-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1, 3-dimethoxypropane, 2-diisobutyl-1, 3-diethoxypropane, 2-diisobutyl-1, 3-dipropoxypropane, 2-isopropyl-2-isopentyl-1, 3-diethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dipropoxypropane, 2-bis (cyclohexylmethyl) -1, 3-diethoxypropane, isobutyltrimethoxysilane, isobutyltriethoxysilane, isopropyltriethoxysilane, tetraethoxysilane and the like.
The molar ratio of the organic aluminum compound to the second external electron donor is 1:1 to 60:1 in terms of aluminum/silicon or aluminum/oxygen, and preferably 5:1 to 30: 1.
According to some embodiments of the present invention, the molar ratio of the second external electron donor to the first external electron donor is from 1 to 30, and preferably from 5 to 30.
In the process of the present invention, it is preferred that the second external electron donor is brought into sufficient contact with the catalyst component in the first-stage reaction product before the second-stage random copolymerization reaction. In some preferred embodiments, the second external electron donor may be added in the feed line after the first stage reactor and before the second stage reactor, or at the front end of the feed line of the second stage reactor, in order to first perform a precontacting reaction with the catalyst in the reaction product of the first stage before the second stage reaction.
Preferably, in the second step, the amount of ethylene is 20-60% of the total volume of ethylene and propylene. In the second step, the volume ratio of hydrogen to the total amount of ethylene and propylene is 0.02 to 1. Meanwhile, as described above, in the first stage, the amount of hydrogen used may be, for example, 0 to 200 ppm. In the second stage, the amount of hydrogen used may be 2000-20000 ppm. In the present invention, control of the composition, structure or properties of the dispersed and continuous phases is important in order to obtain an impact-resistant polypropylene material having high melt strength, as well as high stiffness and toughness. The present invention can prepare the impact polypropylene material with molecular weight distribution, ethylene content of rubber phase and thus better performance.
In a preferred embodiment of the present invention, the yields of the first random copolymerized polypropylene and the second random copolymerized polypropylene are 40:60 to 60: 40. The yield ratio of the propylene-ethylene copolymer rubber dispersed phase to the random copolymerized polypropylene continuous phase is 11-80: 100.
The polymerization reaction of the first step may be carried out in liquid-liquid phase, or in gas-gas phase, or using a combination of liquid-gas techniques. When liquid phase polymerization is carried out, the polymerization temperature is 0-150 ℃, preferably 60-100 ℃; the polymerization pressure should be higher than the saturation vapor pressure of propylene at the corresponding polymerization temperature. The polymerization temperature in the gas phase polymerization is 0 to 150 ℃, preferably 60 to 100 ℃; the polymerization pressure may be normal pressure or higher, and preferably 1.0 to 3.0MPa (gauge pressure, the same applies hereinafter).
The polymerization reaction of the second step is carried out in the gas phase. The gas phase reactor may be a gas phase fluidized bed, a gas phase moving bed, or a gas phase stirred bed reactor. The polymerization temperature is preferably 0 to 150 ℃ and more preferably 60 to 100 ℃. The polymerization pressure is any pressure below the partial pressure of the propylene at which it liquefies.
According to a preferred embodiment of the invention, the reaction temperature in the first stage is between 50 and 100 ℃, preferably between 60 and 85 ℃; the reaction temperature of the second stage is 55-100 ℃, preferably 60-85 ℃; the reaction temperature in the second step is 55-100 deg.C, preferably 60-85 deg.C.
In a preferred embodiment of the present invention, the method of the present invention further comprises further modifying the prepared impact polypropylene material with an alpha or beta crystal nucleating agent to increase the rigidity or toughness of the polypropylene resin material. Suitable alpha crystal and beta crystal nucleating agent modification is well known in the art. The ratio of the weight of the nucleating agent to the total weight of the polypropylene is usually (0.005-3): 100.
According to the process of the present invention, the polymerization reaction may be carried out continuously or batchwise.
In the preparation method of the impact-resistant polypropylene material, the added second external electron donor can react with the catalytic activity center in the copolymerization product material of propylene and ethylene and/or butylene in the first stage to generate a new catalytic activity center, and the propylene and ethylene and/or butylene are continuously initiated to polymerize into a random copolymerization polymer with a molecular weight which is greatly different from that of the product obtained in the first stage in the second stage. The second external electron donor has higher hydrogen response than the first external electron donor, and can prepare a high melt index polymer in the presence of a small amount of hydrogen. And then controlling the molecular weight of the obtained polymer by controlling the reaction conditions of the second-step polymerization reaction, wherein the step is very important, and the second external electron donor with good hydrogen regulation sensitivity added in the second stage in the first step is utilized to obtain the rubber phase molecular weight matched with the continuous phase under a specific hydrogen concentration, so that the polypropylene material with good performance is obtained, which is one of the outstanding advantages of the invention. The composition and structure control of the rubber phase component ensures that the rubber phase component has high melt strength, the specific content of the rubber component ensures that the rubber phase component has higher impact resistance, and in addition, the proper molecular weight distribution also ensures that the polymer has good processability. That is, the invention obtains the polypropylene material with excellent performance by setting a plurality of propylene random copolymerization reaction stages to prepare the continuous phase and selecting the appropriate reaction parameters and reaction conditions of the preparation steps of the continuous phase and the rubber dispersed phase to regulate and control the structure and the performance of the generated continuous phase and the rubber dispersed phase and the combination relationship of the continuous phase and the rubber dispersed phase.
The impact-resistant polypropylene material provided by the invention has the characteristics of high melt strength, high rigidity, high toughness and easiness in heat sealing, so that the impact-resistant polypropylene material is an excellent material suitable for the fields of automobile parts, medical instruments, household articles and the like. The preparation method of the high-melt-strength impact-resistant polypropylene material provided by the invention is simple and effective and is easy to operate.
Detailed Description
The invention will now be further described by way of specific examples, which are not to be construed as limiting the invention in any way.
The polymer related data in the examples were obtained according to the following test methods:
① content of xylene solubles at room temperature and ethylene content in xylene solubles at room temperature (i.e., characterizing the content of the rubber phase and the ethylene content of the rubber phase), were measured by the CRYSTEX method using a CRYST-EX instrument (CRYST-EXEQUIPMENT, IR 4) manufactured by the company PolymerChar, Spain+Detector), a series of samples with different room temperature xylene soluble content are selected as standard samples for correction, and the room temperature xylene soluble content of the standard samples is measured by adopting ASTM D5492. The infrared detector carried by the instrument can detect the weight content of the propylene in the soluble substance and is used for representing the ethylene content (ethylene content in a rubber phase) in the xylene soluble substance at room temperature, namely 100 percent to the weight content of the propylene.
② the tensile strength of the resin is measured according to GB/T1040.2 method.
③ melt mass flow rate (also known as melt index, MFR): the measurement was carried out at 230 ℃ under a load of 2.16kg using a melt index apparatus of type 7026 from CEAST, according to the method described in ASTM D1238.
Bending modulus: measured according to the method described in GB/T9341.
Impact strength of the simply supported beam notch: measured according to the method described in GB/T1043.1.
Sixthly, the content of ethylene: measuring by infrared spectroscopy (IR) method, and calibrating with standard sample measured by nuclear magnetic resonance method. The NMR method was carried out using an AVANCEIII400MHz NMR spectrometer (NMR), 10 mm probe, from Bruker, Switzerland. The solvent is deuterated o-dichlorobenzene, about 250mg of the sample is placed in 2.5ml of deuterated solvent, and the sample is dissolved by heating in an oil bath at 140 ℃ to form a uniform solution. And (3) acquiring 13C-NMR (nuclear magnetic resonance), wherein the probe temperature is 125 ℃, 90-degree pulses are adopted, the sampling time AQ is 5 seconds, the delay time D1 is 10 seconds, and the scanning times are more than 5000 times. Other manipulations, spectral peak identification, etc. were performed as required for commonly used NMR experiments.
Content of butylene: measuring by infrared spectroscopy (IR) method, and calibrating with standard sample measured by nuclear magnetic resonance method. The NMR method was carried out using an AVANCEIII400MHz NMR spectrometer (NMR), 10 mm probe, from Bruker, Switzerland. The solvent is deuterated o-dichlorobenzene, about 250mg of the sample is placed in 2.5ml of deuterated solvent, and the sample is dissolved by heating in an oil bath at 140 ℃ to form a uniform solution. And (3) acquiring 13C-NMR (nuclear magnetic resonance), wherein the probe temperature is 125 ℃, 90-degree pulses are adopted, the sampling time AQ is 5 seconds, the delay time D1 is 10 seconds, and the scanning times are more than 5000 times. Other manipulations, spectral peak identification, etc. were performed as required for commonly used NMR experiments. References include EricT. Hsieh, and James C. randall, Ethylene-1-ButeneCoopomers.1. Comonomer sequence distribution, Macromolecules,15, 353-.
Melt strength of the melt: a Rheotens melt Strength Meter manufactured by Geottfert WerkstoffPruefMaschinen, Germany was used. After the polymer is melted and plasticized by a single screw extruder, a melt bar is extruded downwards by a 90-degree steering head provided with an 30/2 length-diameter-ratio die, the bar is clamped between a group of two rollers which rotate oppositely at constant acceleration to carry out uniaxial stretching, the force in the melt stretching process is measured and recorded by a force measuring unit connected with the stretching rollers, and the maximum force value measured when the melt is stretched until the melt is broken is defined as the melt strength.
⑨ molecular weight Polydispersity Index (PI) resin samples were molded into 2mm sheets at 200 deg.C, subjected to dynamic frequency scanning at 190 deg.C under nitrogen using an ARES (advanced rheometer extension system) rheometer from Rheometric scientific Inc, parallel plate clamps were selected, appropriate strain amplitude was determined to ensure that the experiment was performed in the linear region, and the change in storage modulus (G '), dissipation modulus (G') and the like with frequency was measured for the samples, the molecular weight polydispersity index PI was 105/GcWherein G isc(unit: Pa) is the modulus value at the intersection of the G '-frequency curve and the G' -frequency curve.
⑩ molecular weight (M)w、Mn) And molecular weight distribution (M)w/Mn，Mz+1/Mw): the molecular weight and molecular weight distribution of the sample were measured by PL-GPC220 gel permeation chromatograph manufactured by Polymer laboratories, UK, or GPCIR apparatus manufactured by Polymer char, Spain (IR5 concentration detector), the chromatographic column was 3 PLgel13umOlexis columns in series, the solvent and mobile phase was 1, 2, 4-trichlorobenzene (containing 250ppm of antioxidant 2, 6-dibutyl-p-cresol), the column temperature was 150 ℃, the flow rate was 1.0ml/min, and the calibration was carried out universally by EasiCalPS-1 narrow distribution polystyrene standard manufactured by PL. The preparation process of the room temperature trichlorobenzene soluble substance comprises the following steps: accurately weighing a sample and a trichlorobenzene solvent, dissolving for 5 hours at 150 ℃, standing for 15 hours at 25 ℃, and filtering by adopting quantitative glass fiber filter paper to obtain a solution of trichlorobenzene soluble matters at room temperature for determination. The content of trichlorobenzene solubles at room temperature was determined by correcting the GPC curve area with polypropylene of known concentration, and the molecular weight data of trichlorobenzene insolubles at room temperature was calculated from the GPC data of the original sample and the GPC data of trichlorobenzene solubles at room temperature.
Example 1
The propylene polymerization reaction is carried out on a polypropylene device, and the main equipment of the device comprises a prepolymerization reactor, a first loop reactor, a second loop reactor and a third gas-phase reactor. The polymerization method and the steps are as follows.
(1) Prepolymerization reaction
The main catalyst (DQC-401 catalyst, supplied by Oda, Beijing, China petrochemical catalyst Co., Ltd.), the cocatalyst (triethylaluminum) and the first external electron donor (diisopropyldimethoxysilane, DIPMS) were precontacted at 6 ℃ for 20min, and then continuously added into a continuous stirred tank type prepolymerization reactor to perform a prepolymerization reactor. The Triethylaluminum (TEA) flow into the prepolymerization reactor was 6.33g/hr, the diisopropyldimethoxysilane flow was 0.3g/hr, the procatalyst flow was 0.6g/hr, and the TEA/DIPMS ratio was 50 (mol/mol). The prepolymerization is carried out in a propylene liquid phase bulk environment, the temperature is 15 ℃, the residence time is about 4min, and the prepolymerization multiple of the catalyst is about 80-120 times under the condition.
(2) The first step is as follows: random copolymerization of propylene and ethylene
The first stage is as follows: the prepolymerized catalyst continuously enters a first loop reactor to complete the random copolymerization reaction of propylene and a small amount of ethylene in the first loop reactor, wherein the ethylene addition amount of the first loop is 10000 ppm. The polymerization temperature of the first loop reactor is 70 ℃, and the reaction pressure is 4.0 MPa; and (3) adding no hydrogen into the feed of the first loop reactor, wherein the concentration of the hydrogen detected by an online chromatographic method is less than 10ppm, so as to obtain the first random copolymerization polypropylene A.
And a second stage: 0.63g/hr of 2, 2-diisobutyl-1, 3-Dimethoxypropane (DIBMP) was added to the second loop reactor connected in series with the first loop reactor and mixed with the reactant stream from the first loop reactor, the TEA/DIBMP ratio was 5(mol/mol), where DIBMP was the second external electron donor. The polymerization temperature of the second loop reactor is 70 ℃, and the reaction pressure is 4.0 MPa; and adding a certain amount of hydrogen along with the propylene feeding, detecting the hydrogen concentration in the feeding to be 1000ppm by using an online chromatographic method, and generating a second random copolymer polypropylene B in the second loop reactor to obtain a random copolymer polypropylene continuous phase containing the first random copolymer polypropylene and the second random copolymer polypropylene.
(3) The second step is that: copolymerization of ethylene-propylene
A certain amount of hydrogen and H is added into the third reactor2/(C2+C3)＝0.06(v/v)，C2/(C2+C3)＝0.4(v/v)(C2And C3Respectively referring to ethylene and propylene), and continuously initiating ethylene/propylene copolymerization reaction in a third reactor, wherein the reaction temperature is 75 ℃, and a propylene-ethylene copolymer rubber disperse phase C is generated.
The final product contains the first random copolymerization polypropylene, the second random copolymerization polypropylene and the propylene-ethylene copolymer rubber disperse phase, and the polymer powder is obtained by removing the activity of the unreacted catalyst by wet nitrogen and heating and drying. The powder obtained by polymerization was added with 0.1 wt% of IRGAFOS168 additive, 0.1 wt% of IRGANOX1010 additive and 0.05 wt% of calcium stearate, and pelletized with a twin-screw extruder. The analysis results of the obtained polymer and the physical properties of the polymer are shown in tables 1 and 2.
Example 2
Example 2 the catalyst, pre-complexation, polymerization process conditions and formulation of the auxiliaries and amounts added were the same as in example 1. The difference from the embodiment 1 is that: the comonomer ethylene in the first and second stages of the first step was changed to 1-butene, the amount of addition in the first and second loop was 10 mol% each. The analysis results of the obtained polymer and the physical properties of the polymer are shown in tables 1 and 2.
Example 3
Example 3 the catalyst, pre-complexation, polymerization process conditions and formulation of the auxiliaries and amounts added were the same as in example 1. The difference from the embodiment 1 is that: in the first step, the comonomer ethylene in the first stage and the comonomer ethylene in the second stage are changed into ethylene + 1-butylene, the ethylene addition amount of the first loop and the ethylene addition amount of the second loop are both 6000ppm, and the 1-butylene addition amount is both 5 mol%. . The analysis results of the obtained polymer and the physical properties of the polymer are shown in tables 1 and 2.
Example 4
Example 4 the catalyst, pre-complexation, polymerization process conditions and formulation of the auxiliaries and amounts added were the same as in example 1. The difference from the embodiment 1 is that: the comonomer ethylene addition in the first and second stages of the first step was changed to 30000 ppm. . The analysis results of the obtained polymer and the physical properties of the polymer are shown in tables 1 and 2.
Example 5
Example 5 the catalyst, pre-complexation, polymerization process conditions and formulation of the auxiliaries and amounts added were the same as in example 1. The difference from the embodiment 1 is that: the amount of hydrogen in the second reactor in the second stage became 10000ppm, and the amount of H in the gas phase reactor in the second stage2/(C2+C3) Adjusted to 0.35(v/v), C2/(C2+C3) Adjusted to 0.3 (v/v). The analysis results of the obtained polymer and the physical properties of the polymer are shown in tables 1 and 2.
Example 6
Example 5 the catalyst, pre-complexing, polymerization process conditions and formulation of the auxiliaries used and the amounts added were the same as in example 1The same is true. The difference from the embodiment 1 is that: the amount of hydrogen in the second reactor in the second stage was changed to 15000ppm, and H in the gas phase reactor in the second stage2/(C2+C3) Adjusted to 0.6(v/v), C2/(C2+C3) Adjusted to 0.2 (v/v). The analysis results of the obtained polymer and the physical properties of the polymer are shown in tables 1 and 2.
From the results shown in tables 1 and 2, it can be seen that the polypropylene material prepared according to the method of the present invention has high melt strength, as well as high tensile strength, flexural modulus and notched impact strength. Therefore, the method provided by the invention can be used for preparing the impact-resistant polypropylene material with high melt strength, high rigidity and high toughness. The polypropylene material with excellent performance has wide application value.
Although the present invention has been described in detail, modifications within the spirit and scope of the invention will be apparent to those skilled in the art. Moreover, it should be understood that the various aspects recited, portions of different embodiments (aspects), and various features recited may be combined or interchanged either in whole or in part. In the various embodiments described above, those embodiments that refer to another embodiment may be combined with other embodiments as appropriate, as will be appreciated by those skilled in the art. Furthermore, those skilled in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention.
Claims (12)
1. A high melt strength impact polypropylene material comprising a continuous random copolymer polypropylene phase and a dispersed propylene-ethylene copolymer rubber phase, wherein the continuous random copolymer polypropylene phase comprises at least a first random copolymer polypropylene and a second random copolymer polypropylene, and the first random copolymer polypropylene and the second random copolymer polypropylene are each independently selected from a propylene-ethylene random copolymer, a propylene-1-butene random copolymer, or an ethylene-propylene-1-butene terpolymer;
the material has a room temperature xylene solubles content of greater than or equal to 10 wt% and less than or equal to 35 wt%; and is
The ratio of the Mw of the room temperature trichlorobenzene soluble matter to the Mw of the room temperature trichlorobenzene insoluble matter is greater than 0.4 and less than or equal to 1.
2. The material according to claim 1, characterized in that it has an ethylene content in the room temperature xylene solubles greater than or equal to 28% by weight and less than 45% by weight.
3. The material according to claim 1 or 2, characterized in that it has an ethylene content of 8-20% by weight; and/or a butene content of 0 to 10% by weight.
4. A material according to any of claims 1-3, characterized in that it has a melt index, measured at 230 ℃, under a load of 2.16kg, of 0.1-15g/10min, preferably 0.1-6g/10 min.
5. A material according to any one of claims 1 to 4, characterized in that it has a molecular weight distribution Mw/Mn lower than or equal to 10 and higher than or equal to 4; mz +1/Mw is 10 or more and less than 20.
6. A material according to any one of claims 1 to 5, wherein the melt index of the first random copolymer polypropylene is less than the melt index of the second random copolymer polypropylene.
7. A material according to any one of claims 1 to 6, wherein the first random copolymer polypropylene has a melt index, measured at 230 ℃ under a load of 2.16kg, of from 0.001 to 0.4g/10 min; a melt index of a random copolymerized polypropylene including the first random copolymerized polypropylene and the second random copolymerized polypropylene, measured at 230 ℃ under a load of 2.16kg, is 0.1 to 15g/10 min; preferably 0.1-6g/10 min; and the weight ratio of the first random copolymerized polypropylene to the second random copolymerized polypropylene is 40:60 to 60: 40.
8. A material according to any one of claims 1 to 7, wherein the random copolymer polypropylene has the following characteristics:
molecular weight distribution Mw/Mn is 6-20, preferably Mw/Mn is 10-16;
the fraction having a molecular weight of more than 500 ten thousand is present in an amount of more than or equal to 1.5% by weight and less than or equal to 5% by weight;
the content of fractions having a molecular weight of less than 5 ten thousand is greater than or equal to 15.0% by weight and less than or equal to 40% by weight;
mz +1/Mn is greater than or equal to 70 and less than 150.
9. A material according to any one of claims 1 to 8, wherein the random copolymer polypropylene continuous phase has an ethylene content of from 0 to 6 wt%; and/or the 1-butene content is 0 to 10% by weight.
10. A material according to any one of claims 1 to 9, wherein the material is prepared by copolymerising propylene in the presence of a first random copolymerised polypropylene to give a random copolymerised polypropylene continuous phase comprising the first random copolymerised polypropylene and a second random copolymerised polypropylene, and then copolymerising propylene-ethylene in the presence of the random copolymerised polypropylene continuous phase to give a material comprising a dispersed propylene-ethylene copolymer rubber phase.
11. The material of any of claims 1-10, wherein the ratio of the melt index of the random copolymerized polypropylene continuous phase to the melt index of the polypropylene material comprising the random copolymerized polypropylene continuous phase and the propylene-ethylene copolymer rubber dispersed phase is greater than or equal to 0.6 and less than 1.
12. A material according to any of claims 1 to 11, wherein the weight ratio of propylene-ethylene copolymer to random copolymer polypropylene continuous phase is from 11 to 80: 100.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106674749A (en) * | 2015-11-06 | 2017-05-17 | 中国石油化工股份有限公司 | Polypropylene blow-molded film and preparation method thereof |
| CN107880405A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of low tension fracture elongation rate impact polypropylene resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106674749A (en) * | 2015-11-06 | 2017-05-17 | 中国石油化工股份有限公司 | Polypropylene blow-molded film and preparation method thereof |
| CN106674749B (en) * | 2015-11-06 | 2019-04-19 | 中国石油化工股份有限公司 | A kind of polypropylene blow moulding film and preparation method thereof |
| CN107880405A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of low tension fracture elongation rate impact polypropylene resin |
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| CN105623103B (en) | 2018-04-10 |
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