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    • 专利摘要:
    propylene homopolymer having high melt strength and method of preparing it. the present invention relates to a process for preparing a high melt strength propylene polymer by direct polymerization, comprising that a high molecular weight propylene polymer containing "very high molecular weight fraction" can be prepared controlling the species and proportions of external electron donors in the ziegler-natta catalyst system at different stages in the reaction according to the requirement for fractions of different molecular weight at the stage of different propylene polymerization of the series operation, and said polymer has excellent mechanical properties, especially with very high melt strength. the present invention also provides a propipel homopolymer with high melt resistance, comprising the following characteristics: (1) the mfr is 0.2-10g / 10min at 230 <198> and with a load of 2.16kg; (2) the molecular weight distribution m ~ w ~ / m ^ n ^ is 6-20; (3) the content of the fraction with a molecular weight greater than 5,000,000 is greater than or equal to 0.8% by weight: (4) m ~ z + 1 ~ / m ~ n ~ is greater than or equal to 70. said homopolymer can be used in the preparation of foam products, thermoforming products, biaxial elastic films, inflation films and inflation shaped products.
    公开号:BR112012018282B1
    申请号:R112012018282
    申请日:2011-01-21
    公开日:2020-04-07
    发明作者:Hu Huijie；Huang Honghong；Xu Huan；Yu Luqiang；Guo Meifang；Yu Peiqian；Zhang Shijun；Liu Tao；Song Wenbo；Wei Wenjun；Zhang Xiaomeng
    申请人:Beijing Res Inst Chemical Ind China Petroleum & Chemical Corp；China Petroleum & Chem Corp；
    IPC主号:
    专利说明:

    Descriptive Report of the Invention Patent for PROPYLENE HOMOPOLYMER WITH HIGH FUSION RESISTANCE, ITS USE AND ITS PREPARATION PROCESS. Technical Field [0001] The present invention relates to a propylene homopolymerization process to prepare polypropylene with high resistance to melting in multi-layers. The present invention also relates to a propylene polymer, and more particularly, a propylene homopolymer with high melt resistance, which is especially suitable for preparing foam products, thermoformed products, biaxial elastic films, inflating films and products inflate molded.
    Background [0002] Propylene homopolymer is widely used in the fields of injection processing, extrusion, insulating tape casting and biaxial elasticity due to its cut structure. However, the common polypropylene molecular chain has a linear structure, which is made up of different amorphous polymers, such as PS polystyrene with a region showing similar properties to rubber elasticity over a wide temperature range. Thus, polypropylene cannot be thermoformed over a wide temperature range. Meanwhile, the polypropylene softening point is close to its melting point. When the temperature is higher the melting point, the melting strength and melting viscosity of the polypropylene will decrease rapidly, thereby causing the following problems including uneven product wall thickness during thermoforming, curling and shrinking of the edges that will appear easily during extrusion, coating and winding, and foam collapse during extrusion foaming etc. In this way, the use of polypropylene in the fields of thermoforming, foaming and
    Petition 870200002598, of 01/07/2020, p. 5/39
    2/24 blow molding is limited. As a result, the development of polypropylene with high melt resistance and good ductility is always a matter of interest. The so-called high melt strength of polypropylene (HMSPP) means that the melt can withstand higher strength in tensile fracture. In general, as for the current propylene homopolymer with a melting point rate (MFR) of about 2g / 10min, its highest melting resistance is up to 0.8 to 1N.
    [0003] The main factor affecting the melting strength of polypropylene is the molecular structure of the polymer, which comprises the size of the molecular weight, the molecular weight distribution, whether the molecular chain comprises long branched chains or not, the length and distribution of branched chains, and so on. Generally, the higher the molecular weight of polypropylene, the higher the melting strength of polypropylene. However, the higher the molecular weight of polypropylene, the more unfavorable it is for the post-processing performance of propylene polymer. In this way, taking into account the current application of the materials, it is desirable to allow polypropylene to have a wider molecular weight distribution. In addition, it is also important to allow the polymer to contain a fraction with a very high molecular weight, which can obviously increase the melt strength of the polypropylene. In order to obtain the best performing propylene polymer, the ideal polymer product should comprise a small amount of polymer fraction with very high molecular weight, a certain amount of polymer fraction with relatively high molecular weight and a large amount of fraction of low molecular weight polymer.
    [0004] The process described for increasing the melting strength of polypropylene generally comprises the method of increasing the weight
    Petition 870200002598, of 01/07/2020, p. 6/39
    3/24 molecular polypropylene, improving molecular weight distribution or introducing branched structures by the polymerization process technology, or the method of mixing polypropylene with other amorphous or low crystalline elastomers and resins during the polymer molding process. Among others, adjusting the polymerization process technology is commonly used, which comprises preparing polypropylene with wide molecular weight distribution using a plurality of reactors or obtaining polypropylene with long branched chains using metallocene catalyst and in-situ polymerization, thereby intensifying the melt strength of the final polymer. The most commonly used method is to prepare polypropylene, with wide molecular weight distribution, using a plurality of reactors, connected to each other, in series. Generally, polypropylene with wide molecular weight distribution (MWD) is obtained by series polymerization in different reactors that are suitable to produce polymers with different molecular weights with different amounts of hydrogen and different copolymerization monomers being selected. For example, one of the reactors is suitable for producing higher molecular weight polymer, while another is suitable for producing lower molecular weight polymer.
    [0005] For example, US6875826 and US7365136, both describe a process for preparing propylene polymers with high melt resistance and wide molecular weight distribution. In the process, the multi-stage propylene or copolymerization homopolymer (in two reactors) is carried out in recycled gas phase polymerization reactors connected to each other in series by selecting a Ziegler-Natta catalyst with lower hydrogen response, wherein said Ziegler-Natta catalyst is first characterized using a cycloalkyl-containing siloxane,
    Petition 870200002598, of 01/07/2020, p. 7/39
    4/24 as dicyclopentyl dimethyl silane, as the external electron donor. Through hydrogen concentration control in each reactor, high molecular weight fraction polypropylene, that is, MFR <0.1g / 10min, is produced in the first stage, with its weight content in a range of 10 to 35 %; low molecular weight fraction polypropylene, that is, MFR> 0.5g / 10min, is produced in the second stage, with its weight content in a range of 65 to 90%; and the MFR of the final polymer is in a range of 0.1 to 20g / 10min. Finally, it is obtained after reacting a linear propylene homopolymer with high resistance to melting and a wide molecular weight distribution (Mw / Mn> 6).
    [0006] As is well known, regarding the polymerization of propylene, the species of the external electron donor will generally influence the stereoregularity and polymer molecular weight distribution significantly. When the above process is used to prepare homopolypropylene with wide molecular weight distribution in a plurality of reactors, it is desirable that the molecular weight and stereoregularity of the high molecular weight fraction, which can determine the mechanical properties of the polymer, are as high as possible, especially with a certain amount of very high molecular weight fraction, while the molecular weight of low molecular weight fraction, which can determine the polymer extrusion properties, is as low as possible and also with a higher content. However, the composition and characteristics of the catalyst are immutable in the two reactors of the above patents. As a result, the reaction response of the catalyst in the molecular weight regulator, ie, hydrogen, is uniform in the two-stage polymerization, which has a certain limitation to control or adjust the properties of polymer chains.
    [0007] Specifically, when the external electron donor with
    Petition 870200002598, of 01/07/2020, p. 8/39
    5/24 lower hydrogen response is used in the catalyst system, the molecular weight of the polymer can be higher in the first stage to produce higher molecular weight fraction. However, when in the second stage to produce the lowest molecular weight fraction, very high hydrogen content is required to meet the current requirement because of its insensitivity to hydrogen. If the external electron donor with the highest hydrogen response is used in the catalyst system, although the amount of hydrogen is low in the second stage to produce a lower molecular weight fraction, the molecular weight cannot be high enough in the first stage to produce higher molecular weight fraction, thereby reducing the mechanical properties of the final products.
    [0008] Furthermore, CN1241196A describes a polypropylene resin composition and the use thereof, in which a two-step method is used to obtain the polypropylene resin composition with high melt stress. In the method, high molecular weight polypropylene is prepared in the first stage without hydrogen, and low molecular weight polypropylene is prepared in the presence of hydrogen in the second stage. One and the same external electron donor, such as dicyclopentyl dimethoxy silane, is used in the entire process. The prepared polypropylene comprises the high molecular weight fraction with a molecular weight higher than 1.5x106. However, it still cannot solve the problems associated with the previous patents.
    [0009] In CN1156999A entitled The Dual Donor Catalyst System for Olefin Polymerization, two different catalysts are used at different stages. Tetraethoxy silane is used as the external electron donor in the first stage, and dicyclopentyl dimethoxy silane is used as the external electron donor in the second stage. Both CN1612901A and US6686433B1 also similarly describe the teachings. The objects of these patents are not for
    Petition 870200002598, of 01/07/2020, p. 9/39
    6/24 obtain macromolecular in order to obtain polypropylene with high resistance to fusion. The process steps of the same similarly comprise: first preparing the minor molecular polypropylene, then preparing the major molecular polypropylene in the second stage, thus obtaining polyolefins with high crystallinity. If using said processes described in these patents to produce polypropylene, said external electron donor with a high hydrogen response, which is added in the first stage to prepare low molecular weight polymer, also works in the second stage, so that molecular overweight cannot be prepared in the second stage. Similarly, the high melt strength propylene homopolymer with advantageous mechanical properties and processing property cannot be obtained according to the above patents.
    [00010] As for the current applications of some polypropylene, such as foaming products, the melt flow rate (MFR) of the same is required to be about 2 to 3 g / 10min. Because of the limitation of the above polymerization processes, the distribution of the three fractions, that is, the very high molecular weight fraction, the high molecular weight fraction and the low molecular weight fraction, in the polymers are not satisfactory. In this way, the properties of the final polymer are impaired to some extent.
    Summary of the invention [00011] In order to solve the problems present in the prior art, the present invention provides a process for preparing propylene homopolymer with high melt resistance through direct polymerization.
    [00012] The inventor found by intensive experiments that a propylene polymer with wide molecular weight distribution and containing very high molecular weight fraction can be prepared
    Petition 870200002598, of 01/07/2020, p. 10/39
    7/24 controlling the species and proportions of the external electron donor in the Ziegler-Natta catalyst system at different reaction stages, preferably in combination with the control of the amount of the regulating molecular weight according to the requirement for different molecular weight fractions in polymerization other than propylene stage of series operations. Said polymer has excellent mechanical properties, especially very high melt strength.
    [00013] The propylene polymerization process of the present invention comprises a propylene homopolymerization reaction of two or more stages carried out in two or more reactors connected in series, in which: in the first stage, in the presence of the Ziegler-Natta catalyst comprising a first external electron donor component, propylene homopolymerization is carried out under a polymerization temperature of 50 to 100 ° C, the MFR of the polymer obtained being controlled within the range of 0.01 to 0.3 g for 10 min; and in the second stage, based on the reagent from the first stage, a second external electron donor component is added to further homopolymerize propylene in the presence of hydrogen; the MFR of the polymer finally obtained is controlled within the range of 0.2 to 10 g for 10 min, in which the hydrogen response of the first external electron donor is lower than that of the second external electronic donor.
    [00014] Preferably, in the first stage, the ZieglerNatta catalyst is composed of the following components: (1) a solid catalyst component with magnesium, titanium, halogen and internal electron donor as the main components; (2) an organic aluminum component; and (3) the first external electron donor component, in which the weight ratio of the component (1) to the component (2), based on the ratio of titanium to aluminum, is 1: 10-500, and the proportion of component weight (2) for component
    Petition 870200002598, of 01/07/2020, p. 11/39
    8/24 (3) is 10-150: 1; and in the second stage, the weight ratio of the organic aluminum component to the second added external electron donor component is 1-50: 1.
    [00015] Preferably, in order to meet the requirements in the different molecular weight fractions, in the first stage, the quantity of the first external electron donor is adjusted in such a way that the weight ratio of the first external electron donor to the organic aluminum is 1: 15-100; and in the second stage, the second external donor component is added with the amount of the organic aluminum component added in the first stage, such that the weight ratio of the second external donor component to the organic aluminum is 1: 2 ~ 20 .
    [00016] Hydrogen adding quantities in the first stage and the second stage is controlled according to the requirements of the final MRF. Preferably, in the first stage, the hydrogen content is less than or equal to 300 ppmV.
    [00017] The first external electron donor component is shown as the general formula R 1 nSi (OR 2 ) 4-n, where R 1 , which can be identical or different from each other, can be groups (C3-C6) branched or cyclized aliphatics, R 2 is (C1-C3) straight chain aliphatic group, such as methyl, ethyl or propyl, and n is 1 or 2.
    [00018] The second external electron donor is shown as the general formula R 3 nSi (OR 4 ) 4-n, where n is 0 or 1 or 2, and R 3 and R 4 , which can be identical to or different each other, can be (C1-C3) straight chain aliphatic groups. Alternatively, the second external electron donor is shown as the general formula R 5 R 6 Si (OR 7 ) 2, where R 5 is (C1-C3) linear chain aliphatic group, R 6 is (C3-C6) groups branched or cyclized aliphatics, and R 7 is (C1-C3) straight chain aliphatic group.
    [00019] The proportion of productivity from the first stage to
    Petition 870200002598, of 01/07/2020, p. 12/39
    9/24 that of the second stage is 30:70 to 70:30, preferably 40:60 to 60:40.
    [00020] In the polymerization process of the present invention, the propylene polymerization catalyst comprises, but is not limited to, Ziegler-Natta catalyst. The Ziegler-Natta catalyst used has been well documented, preferably the catalyst with high stereoselectivity. The said Ziegler-Natta catalyst with high stereoselectivity here means that you can prepare propylene homopolymer with an isostatic index of more than 95%. Such a catalyst generally comprises: (1) solid catalyst component, preferably active Ti-containing solid catalyst component, (2) organic aluminum compound cocatalyst component, and (3) external electron donor component.
    [00021] Specific examples comprising such an active solid catalyst component (1) can be found in CN85100997, CN98126383.6, CN98111780.5, CN98126385.2, CN93102795.0,
    CN00109216.2, CN99125566.6, CN99125567.4 and CN02100900.7. Said catalyst can be used directly, or added after pre-complexation and / or pre-polymerization. The catalysts described in CN85100997, CN93102795.0, CN98111780.5 and CN02100900.7 are particularly advantageous when used in the process of preparing high melt strength polypropylene of the present invention.
    [00022] The cocatalyst component (2) of the present invention is the organic aluminum compound, preferably composed of alkyl aluminum, more preferably trialkyl aluminum, such as triethyl aluminum, triisobutyl aluminum and tri-n-butyl aluminum, where the proportion of the aluminum component solid catalyst containing Ti for the organic aluminum cocatalyst component, based on the weight ratio of Al to Ti, is 10-500: 1.
    Petition 870200002598, of 01/07/2020, p. 13/39
    10/24 [00023] The external electron donor with different properties is added in different reactors according to the requirement for different molecular weight fractions. Specifically, according to the present invention, it needs to prepare propylene polymer with high molecular weight fraction in the first stage, that is, in the first reactor; then, the external electron donor with the lowest hydrogen response is selected so as to enable the said fraction having an even higher molecular weight. The outer electron is shown as the general formula R1nSi (OR 2 ) 4-n, where R 1 , which can be identical to or different from each other, can be branched or cyclized aliphatic groups (C3-C6), and preferably, for example, cyclopentyl, iso-propyl or cyclohexyl, R 2 is linear aliphatic (C1-C3) group, such as methyl, ethyl or propyl, and n is 1 or 2, preferably 2. Specific compounds may comprise dicyclopentyl dimethoxy silane , diisopropyl dimethoxy silane, dicyclohexyl dimethoxy silane, diisobutyl dimethoxy silane, and so on.
    [00024] Preferably, the first outer electron is dicyclopentyl dimethoxy silane and / or diisopropyl dimethoxy silane.
    [00025] The MFR of the polymer obtained in the first stage is controlled within a range of 0.01 to 0.3 g for 10 min. According to actual needs, it is common to select that no additional regulatory molecular weight or a very small amount of hydrogen (less than or equal to 300 ppmV) is added as the regulatory molecular weight in the first reactor in order to obtain the molecular weight fraction high.
    [00026] Based on the first stage polymerization reagent, a second external electron donor component and a molecular weight regulator (hydrogen) are added for the second homopolymerization stage, and the MFR of the finally obtained polymer is controlled within the range from 1 to 10g for 10 min.
    Petition 870200002598, of 01/07/2020, p. 14/39
    11/24 [00027] The second external electron donor component is shown as the general formula R3nSi (OR 4 ) 4-n, where n is 0 or 1 or 2, and R3 and R 4 , which can be identical to or different from each other, they may be (C1-C3) straight chain aliphatic groups, such as methyl, ethyl or propyl. According to specific external donors they may comprise, but are not limited to, tetramethoxy silane, tetraethoxy silane, trimethyl methoxy silane, trimethyl ethoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane, and so on. Alternatively, the second external electron donor component is shown as the general formula R5R6Si (OR 7 ) 2, where R5 is (C1-C3) straight chain aliphatic groups, such as methyl, ethyl or propyl, R6 is (C3- C6) branched or cyclized allyphatic group, R 7 is (C1-C3) linear chain aliphatic group. Specific compounds can be, for example, methyl cyclohexyl dimethoxy silane.
    [00028] Preferably, the second external electron donor is tetraethoxy silane and / or methyl cyclohexyl dimethoxy silane.
    [00029] Said polymerizations of different stages are carried out in different reactors respectively in the polymerization process of the present invention. A specific modality is that, polymerization in the first stage is carried out in the first reactor, and polymerization in the second stage is carried out in the second reactor. In the first reactor, (1) a solid catalyst component with magnesium, titanium, halogen and an internal electron donor as the main components; (2) an organic aluminum component; and (3) the first external electron donor component is added, and the homopolymerization of propylene is carried out substantially without hydrogen. The obtained polymerization products are introduced in the second reactor, in which the second external electron donor component is added, and homopolymerization of propylene is still carried out in the presence of a certain amount of hydrogen.
    [00030] Said three catalyst components can be
    Petition 870200002598, of 01/07/2020, p. 15/39
    12/24 added directly to the first reactor, or added to that leg after pre-complication and / or pre-polymerization known in the art. The pre-complexation reactor can be of several types, to achieve a sufficient and effective mixture of each catalyst component. The preconditioning reactor can be a continuously agitated tank reactor, a reactor with tubular recycle, a section of piping comprising a static mix, or even a section of piping in which the materials are in a turbulent state. [00031] The pre-complexation temperature is controlled within 10 to 60 ° C, and preferably within 0 to 30 ° C. The pre-complexing time is controlled within 0.1 to 180 min, and preferably within 5 to 30 min.
    [00032] The catalyst with or without precomplexation can optionally be prepolymerized. Prepolymerization can be carried out continuously in the liquid phase, or intermittently in an inert solvent. The prepolymerization reactor can be a continuously agitated tank, a reactor with tubular recycle, and so on. The polymerization pre-temperature is controlled within -10 to 60 ° C, and preferably within 0 to 40 ° C. Multiple prepolymerization is controlled within 0.5 to 1000 times, and preferably within 1.0 to 500 times.
    [00033] Said polymerization can be carried out in the liquid propylene phase, or in the gas phase, or using combined liquid-gas technology. When liquid phase polymerization is carried out, the polymerization temperature is 0 to 150 ° C, preferably 40 to 100 ° C, and the polymerization pressure should be higher than the saturated vapor pressure of propylene at the corresponding polymerization temperature. In gas polymerization, the polymerization temperature is 0 to 150 ° C, preferably 40 to 100 ° C, and the polymerization pressure can be the normal or higher pressure, preferably 1.0 to 3.0 MPa (pressure of
    Petition 870200002598, of 01/07/2020, p. 16/39
    13/24 caliber, the same below).
    [00034] Polymerization can be carried out continuously or intermittently. Continuous polymerization can be carried out on two or more liquid phase reactors or gas phase reactors that are connected in series, where the liquid phase reactor can be a reactor with tubular recycle or a stirring tank reactor, and the rector gas phase can be a horizontal stirred bed reactor or a vertical stirred bed reactor. The liquid phase reactor mentioned above and the gas phase reactor can be combined together in any appropriate manner. The homopolymerization of propylene is preferably carried out in two or more reactors with tubular recycle connected in series.
    [00035] The polymer obtained in the present invention can be extruded and granulated using appropriate equipment. During granulation, additives commonly used in the field as an antioxidant, light stabilizer, heat stabilizer, dye and filler are generally added.
    [00036] In the polymer preparation process of the present invention, adjusting the quantity and species of external electron donors and the quantity of hydrogen that are added in the two reactors connected in series or at different stages in intermittent operation, without the need for a specific catalyst , nor any multi-functional copolymerization monomer should be added. Compared with the conventional process of adjusting the molecular weight distribution of the polymer only by different hydrogen concentration, a higher molecular weight component can be obtained with less hydrogen in accordance with the present invention. As a result, products with better performance can be prepared in a more cost effective way.
    [00037] By means of the polymerization process of the present invention, propylene polymer with wide weight distribution
    Petition 870200002598, of 01/07/2020, p. 17/39
    Molecular 14/24 can be obtained, and the characteristic of it first of all is that the content of the very high molecular fraction is higher and at the same time the content of the low molecular weight fraction is also beyond a certain amount. As such, the melting strength of the propylene polymer is significantly increased, and the processing performance of the polymer can be guaranteed.
    [00038] The most specific process for preparing propylene homopolymer with high melt resistance, in the present invention, is characterized by the fact that a two-stage propylene homopolymerization reaction is carried out in two reactors with tubular recycle connected in series, in which : in the first stage, in the presence of Ziegler-Natta catalyst, the propylene homopolymerization reaction is carried out at a polymerization temperature of 50 to 100 ° C with a hydrogen content of less than or equal to 300 ppmV, the MFR of the polymer obtained being controlled within 0.01 to 0.3 g / 10min, and said Ziegler-Natta catalyst is composed of the following components: (1) a solid catalyst component with magnesium, titanium, halogen and an internal electron donor as the main components, (2) an organic aluminum component, and (3) dicyclopentyl dimethoxy silane, in which the weight ratio of component (1) to component (2), based on the prop titanium to aluminum ratio is 1: 10-500, and the weight ratio of component (2) to component (3) is 10-150: 1; and in the second stage, based on the first stage reagent, tetraethoxy silane is added in the presence of hydrogen to further propylene homopolymerization, and the amount of tetraethoxy silane is determined according to the amount of the organic aluminum component added in the first stage, so that the weight ratio of that to organic aluminum is 1: 1 ~ 50, the MFR of the final polymer being controlled within 0.2 to 10 g / 10min.
    [00039] The present invention further provides a homopolymer of
    Petition 870200002598, of 01/07/2020, p. 18/39
    15/24 corresponding propylene with high melt resistance, comprising the following characteristics:
    [00040] the MFR is 0.2-10 g / 10 min at 230 ° C with a load of 2.16 kg, [00041] the molecular weight distribution Mw / Mn is 6-20, [00042] the content of the fraction with a higher molecular weight than
    5,000,000 is higher than or equal to 0.8% by weight, (4) Mz + 1 / Mn is higher than or equal to 70.
    [00043] It is necessary to increase the molecular weight of the polymer to increase the melt strength of the polymer. However, in order to ensure that the product has excellent processing performance, it is critical to control the molecular weight distribution within a region of a certain average molecular weight, that is, a certain MFR. In the polymer, on the one hand, it needs to have a certain amount of very high molecular weight fraction, and on the other hand, it also needs to have a large amount of low molecular weight fraction, that is, it needs a wider region of molecular weight distribution.
    [00044] As is well known, macromolecular is not composed of a compound with a single molecular weight. Even a type of pure macromolecular is also composed of mixtures of the same series of polymers having the same chemical component, different molecular weights and different structures. The property that the macromolecular has uneven molecular weights, that is, the molecular weight size is different, is called polydispersity of molecular weight. Generally, the measured molecular weight of macromolecular is the average molecular weight. The average molecular weight of the polymer is the same, but its polydispersity is not necessarily the same. Generally speaking, gel permeation chromatography is used to measure the molecular weight distribution of the polymer, and then the average number of molecular weight, the average weight of molecular weight, Z the average molecular weight and Z + 1 average weight molecular can be
    Petition 870200002598, of 01/07/2020, p. 19/39
    16/24 obtained according to the molecular weight curve distribution. The weights of the high molecular weight fraction in the average high molecular weight values are different, and they meet the following relationship: Mn <Mw <M z <M z +1. Generally, Mw / Mn is used to express the molecular weight distribution of the polymer, where Mn is close to the low molecular weight part of the polymer, that is, the effect of part of the low molecular weight on Mn is greater, and Mw is close of the high molecular weight part of the polymer, that is, the effect of the high molecular weight part in Mw is greater. In order to enable polypropylene to have better full performance or processing performance, the molecular weight distribution of the propylene polymer, that is, Mw / Mn, is generally controlled within 6 to 20.
    [00045] However, the inventor found, after intensive experiments, that he cannot meet the requirements to achieve high melt strength just by controlling the Mw / Mn data, and he also has to quantitatively control the very high molecular weight fraction within a certain range. It is especially preferred quantitatively to control both the very high molecular weight fraction and the low molecular weight fraction within a certain range respectively. Bearing in mind that a small amount of the very high molecular weight fraction does not affect Mw significantly, but it does affect Mz + 1 significantly, and a large amount of low molecular weight affects Mn greatly, it is very important to ensure that Mz + 1 / Mn is superior or equal to 70 in the propylene polymer of the present invention.
    [00046] In the propylene homopolymer above the present invention, the fraction content with a molecular weight greater than 5,000,000 is preferably higher than or equal to 1.0% by weight, and more preferably greater than or equal to 1, 5% by weight. Preferably, Mz + 1 / Mn is higher than or equal to 80. The fraction content with a weight
    Petition 870200002598, of 01/07/2020, p. 20/39
    Molecular 17/24 less than 50,000 is preferably greater than or equal to 15.0% by weight and less than or equal to 40.0% by weight, and more preferably greater than or equal to 17.5% by weight and less than or equal to 30.0% by weight. [00047] Preferably, the MFR of the propylene homopolymer is 1.6 to 6 g / 10 min, and more preferably 2.5 to 6 g / 10 min, at 230 ° C with a load of 2.16 kg.
    [00048] In addition, polymer with a PI polydispersity index of 6.0-20.0, preferably 9.0-16.0, is obtained in the present invention by controlling each fraction of molecular weight.
    [00049] The melting point Tm of the propylene homopolymer in the present invention is greater than or equal to 163 ° C, and the peak temperature of the clearance curve raising the ATREF temperature, that is, Tpicoatref, is greater than or equal to 122 °. Ç. The content of substances soluble in xylene is less than or equal to 4% by weight.
    [00050] The high melt strength propylene homopolymer of the present invention preferably comprises the following characteristics:
    [00051] MFR is 0.2 to 10 g / 10min, preferably 1.6 to 6 g / 10min, at 230 ° C with a load of 2.16kg, [00052] the molecular weight distribution Mw / Mn is 6- 20, [00053] the fraction content with a molecular weight greater than 5,000,000 is greater than or equal to 0.8% by weight, preferably greater than or equal to 1.0% by weight, [00054] to Mz + 1 / Mn is greater than or equal to 70, preferably greater than or equal to 80.
    [00055] More preferably, said propylene homopolymer comprises the following characteristics:
    [00056] MFR is 1.6 to 6 g / 10min at 230 ° C with a load of 2.16kg, [00057] the molecular weight distribution Mw / Mn is 6-20, [00058] the fraction content with a molecular weight greater than 5,000,000
    Petition 870200002598, of 01/07/2020, p. 21/39
    18/24 is greater than or equal to 1.0% by weight, [00059] Mz + i / Mn is greater than or equal to 80, [00060] the fraction content with a molecular weight less than 50,000 is greater than or equal to 17 , 5% by weight and less than or equal to 30.0% by weight, [00061] the polydispersion index of polymer PI is 9-16.
    [00062] The polymer of the present invention has a melt strength greater than that of the prior art. The melt strength is greater than 0.8 N, even greater than 2.2 N. The polymer of the present invention is mainly used to prepare foam products, biaxial elastic films, thermoforming products and molded inflating products.
    Specific Modes of the Invention [00063] In the following the present invention will be described in more detail with specific examples, which should be interpreted only as explaining the present invention, but not limiting the scope of the present invention.
    [00064] The data related to polymers in the examples are obtained using the following test methods.
    [00065] The thermoforming temperature is measured according to ASTM D648-07.
    [00066] Fusion strength is measured by the Rheoten Melt Strength Meter produced by Geottfert Werkstoff Pruefmaschinen, Germany. Said meter comprises a pair of rollers rotating in opposite directions. The polymer is melted and plasticized using a single screw extruder, then extruded from a die head with a 90 ° stirring. Subsequently, the polymer is fixed between two rollers and uniaxially extracted in a manner of constant acceleration. The stress is measured by a corresponding component to measure the force. The value of the maximum force measured from the start of the
    Petition 870200002598, of 01/07/2020, p. 22/39
    19/24 fusion fracture is called fusion resistance.
    [00067] The melt flow rate (MFR) is measured according to ISO1133 at 230 ° C with a load of 2.16 kg.
    [00068] Regarding the molecular weight polydispersity index, ie PI, first the rheometer with the ARES type, ie Advanced Rheometer Extension System, sold by Rheometric Scientific Inc., United States, is used to measure the values viscosity and sample module at 190 ° C and within a certain frequency range, in which the sample sample is maintained through a flatbed type accessory. The molecular weight polydispersity index, ie PI, is equal to 105 / G, where G is the value of the module at the intersection point of the storage module's frequency curve (G ') - and the frequency curve of the loss module (G) -. The resin sample is molded on a 2 mm plate at 200 ° C before being measured.
    [00069] Regarding the molecular weight distribution (Mw / Mn, Mz + 1 / Mn), the gel permeation chromatography PL-GPC220 produced by Polymer Laboratories, Inc., England, and the IR5 detector produced by Polymer Char Inc. , Spain, are used to measure the molecular weight and molecular weight distribution of the sample, where the chromatography columns are three Plgel 10pm MIXED-B columns connected in series, the solvent and the fluid phase is 1,2, 4-trichlorobenzene (comprising 0.3 g / 1000 mL of antioxidant and 2,6-dibutyl pcresol), the column temperature is 150 ° C, and the flow rate is 1.0 ml / min. [00070] The tensile strength of the resin is measured according to ASTM D638-00.
    [00071] The flexural strength and flexural modulus of the resin are measured according to ASTM D790-97.
    [00072] IZOD bevel impact resistance is measured according to ASTM D256-00.
    [00073] Intrinsic viscosity is measured according to ASTM D
    Petition 870200002598, of 01/07/2020, p. 23/39
    20/24
    5225-1998 using Y501C intrinsic viscosity analyzer produced by VISCOTEK Inc., United States. The solvent is decalin, and the test temperature is 135 ° C.
    [00074] The content of soluble substances is measured using the CRYSTEX instrument produced by PoliChar, Inc., Spain, and the solvent is trichlorobenzene. The result is corrected by the refrigerated soluble xylene substance data of the polymer measured according to the ASTM D5492-2006 standard.
    Example 1 [00075] Polymerization is carried out in a polypropylene pilot plant. Its main equipment comprises a prepolymerization reactor, a first reactor with tubular recycling and a second reactor with tubular recycling. The polymerization process and its steps are as follows.
    Prepolymerization [00076] The main catalyst, that is, the active component of solid catalyst containing titanium, is obtained using the method described in Example 1 of CN93102795, in which the Ti content is 2.4% by weight, the content Mg is 18.0% by weight, and the dibutyl phthalate content is 13% by weight.
    [00077] The main catalyst, the cocatalyst (triethyl aluminum) and the first external electron donor (dicicylpentyl dimethoxy silane, DCPMS) are pre-contacted with each other at 10 ° C for 20 min, and then continuously added in the pre reactor -polymerization for prepolymerization. Prepolymerization is carried out on the mass of the liquid propylene phase, where the temperature is 15 ° C, the residence time is about 4 min, and the multiple propolymerization of the catalyst is about 120 to 150 times under such conditions. In the prepolymerization reactor, the flow rate of triethyl aluminum is 6.33g / hour, the flow rate of dicicylpentyl dimethoxy silane is 0.33g / hour, and the flow rate of the main catalyst is about 0.01g / hour.
    Petition 870200002598, of 01/07/2020, p. 24/39
    21/24
    Homopolymerization of propylene [00078] After prepolymerization, the catalyst flows into two reactors with tubular recycle connected in series, in which the homopolymerization of propylene is completed. The reaction temperature of the two reactors with tubular recycle is 70 ° C, and their reaction pressure is 4.0 MPa. The processing conditions of the reactor with tubular recycle are controlled to reach the ratio of productivity of the first reactor with tubular recycle to that of the second reactor with tubular recycle of about 45:55.
    [00079] No hydrogen is added to the feed for the first reactor with tubular recycle, and the hydrogen content measured by line chromatography (online) is less than 10 ppmV. A certain amount of hydrogen is added to the feed for the second reactor with tubular recycle, and the hydrogen content measured by line chromatography is 4500 ppmV.
    [00080] As the catalyst components are added directly to the first reactor with tubular recycle after prepolymerization, there is no other supply for the first reactor with tubular recycle except propylene. As a result, the weight ratio of triethyl aluminum to dicyclopentyl dimethoxy silane in the first reactor with tubular recycle (hereinafter referred to as Al / SiI) is that in the catalyst prepolymer, that is, 19.0.
    [00081] Tetraethoxy silane (TEOS) with a flow rate of 0.67g / hour is supplemented in the second reactor with tubular recycle. In this way, the weight ratio of triethyl aluminum to tetraethoxy silane in the second reactor with tubular recycle (hereinafter referred to as Al / Si-II) is 9.4. The specific process conditions are shown in Table 1.
    [00082] Then the propylene is instantaneously separated from the polymer of the second reactor with tubular recycle, the activity of the catalyst in the
    Petition 870200002598, of 01/07/2020, p. 25/39
    22/24 reactor is eliminated by wet nitrogen. Then, the polymer powders are obtained after heating and drying the polymer.
    [00083] 0.1% by weight of additive IRGAFOS 168, 0.2% by weight of additive IRGANOX 1010 and 0.05% by weight of calcium stearate are added in the powders obtained by the polymerization, and then the mixture is granulated through of a double screw extruder. The properties of the obtained granules are tested according to the existing ASTM standard. Example 2 [00084] Example 2 differs from Example 1 in that: a small amount of hydrogen is added to the propylene supplement feed of the first reactor with tubular recycle, and the hydrogen content is measured by line chromatography is 230 ppmV; the amount of hydrogen feed in the propylene supplement food in the second reactor with tubular recycle is adjusted to 8500 ppmV; Al / Si-I is adjusted to 45 (weight: weight) and Al / Si-II is adjusted to 4.2 (weight: weight) by adjusting the amount of food for external electron donors; and the amount of the added triethyl aluminum cocatalyst is immutable.
    Example 3 [00085] Example 3 differs from Example 2 only in that the Al / Si-I is set to 85 (weight: weight) by adjusting the amount of feed from the external electron donors, while the amount of triethyl aluminum added cocatalyst is immutable. Example 4 [00086] Example 4 differs from Example 3 only in that the amount of hydrogen in the propylene supplement feed of the second reactor with tubular recycle is adjusted to 12000 ppmV. Example 5 [00087] Example 5 differs from Example 2 only in that the tetraethoxy silane in the second reactor with tubular recycle is exchanged for
    Petition 870200002598, of 01/07/2020, p. 26/39
    23/24 methyl cyclohexyl dimethoxy silane (CHMMS), the amount of addition is 1.51 g / hour, Al / Si-II is 4.2 (weight: weight), and Al / Si-I in first reactor with tubular recycle is set to 60.
    [00088] The specific processing parameters, the results of the polymer analysis obtained and the physical polymer properties of each example are listed in Tables 1 to 4.
    Table 1 The conditions of the polymerization process in the Examples
    Processing conditions Example 1 Example 2 Example 3 Example 4 Example 5 External electron donor First reactor DCPMS DCPMS DCPMS DCPMS DCPMS Second reactor TEOS TEOS TEOS TEOS CHMMS Al / Si First reactorAl / Si-I p / p 19 45 85 85 60 Second reactorAl / Si-II p / p 9.4 4.2 4.2 4.2 4.2 FoodH 2 First reactor ppmV 0 230 230 230 230 Second reactor ppmV 4500 8500 8500 12000 8500
    Table 2 The results of the polymer analysis in Examples (1)
    MFR (g / min) Intrinsic viscosity(dl / g) Content of soluble substances (% by weight) First reactor Second reactor First reactor Second reactor First reactor Second reactor Example 1 0.03 1.6 5.9 3.4 3.0 2.4 Example 2 0.08 2.7 5.3 2.8 4.4 2.8 Example 3 0.08 3.0 5.2 2.7 4.7 3.3 Example 4 0.08 3.9 5.1 2.4 5.0 2.6 Example 5 0.08 1.9 5.0 3.2 4.4 3.2
    Table 3 The results of the polymer analysis in Examples (2)
    No. GPC rheological method Mn, 10 4 Mw, 10 4 Mz, 10 4 Mz + 1, 10 4 Mw / Mn Mz + 1 /Mn 10 3 <M <5x10 4 fraction content (% by weight) M> 5x10 6 fraction content (% by weight) PI Example 1 5.9 66.5 282.9 511.0 11.2 86.3 17.8 1.86 15.0 Example 2 4.4 51.5 24.3 512.1 11.1 115.5 20.9 1.14 9.3 Example 3 4.4 53.5 28.8 581.9 12.1 131.7 23.1 1.61 13.7 Example 4 3.2 49.6 229.3 481.8 15.6 151.9 22.0 0.98 8.6 Example 5 3.7 49.7 205.5 427.7 13.6 116.5 19.0 0.81 7.1 Commercial F280z 4.4 43.3 166.2 385.8 9.8 87.70.46 4.6 Commercial T38F 7.0 40.3 121.3 253, 3 5.8 36.20.15 4.1
    Note: F280z is the polypropylene produced by Zhenhai Refining and
    Petition 870200002598, of 01/07/2020, p. 27/39
    24/24
    Chemical Branch of China Petroleum & Chemical Co., Ltd .; and T38F is the polypropylene produced by Hunan Changsheng petrochemical Co., Ltd. Table 4 The physical properties of polymers of the Examples
    MFR Tension Resistance Flexural Strength Flexion Module Fusion resistance Thermal forming temperature IZOD notch resistance impact (J / m)g / 10 min MPa MPa GPa N 0.46kg load, ° C Normal temperatures -20 o C Example 1 1.6 40.2 57.0 2.24 2.20 116.0 40.2 19.1 Example 2 2.7 38.7 50.9 1.87 1.00 103.2 39.4 19.1 Example 3 3.0 38.4 48.2 1.79 1.30 98.9 34.7 19.1 Example 4 3.9 38.8 48.1 1.80 0.95 99.6 33.1 18.8 Example 5 1.9 35.7 44.4 1.60 0.90 96.7 42.2 19.7 CommercialF280z 3.0 0.4 CommercialT38F 3.0 0.31
    Petition 870200002598, of 01/07/2020, p. 28/39
    权利要求:
    Claims (14)
    [1]
    (1) the MFR is 0.2-10g / 10 min at 230 ° C with a load of 2.16 kg;
    (1) a solid catalyst component with magnesium, titanium, halogen and an internal electron donor as the main components;
    (1) a solid catalyst component with magnesium, titanium, halogen and an internal electron donor as the main components;
    1. Process for preparing propylene homopolymer with high melt resistance, characterized by the fact that a propylene homopolymerization reaction of two or more stages is carried out in two or more reactors connected in series, and in the first stage, in the presence of a Ziegler-Natta catalyst comprising a first external electron donor component, propylene homopolymerization reaction is carried out under a polymerization temperature of 50100 ° C, the melt flow rate (MFR) of the polymer obtained being controlled within a range 0.01-0.3g per 10 min, the hydrogen content being less than or equal to 300 ppm V, and in the second stage, based on the first stage reagent, a second external electron donor component is added to still perform the homopolymerization of propylene in the presence of hydrogen and the MFR of the polymer finally obtained is controlled within a range of 0.2-10g by 10 min, with the hydrogen response of the first external electron donor being lower than that of the second external electronic donor, with the productivity ratio of the first stage to the second stage being 30:70 to 70:30, being that the first external electron donor component is shown as the general formula
    R 1 nSi (OR 2 ) 4-n, in which
    R 1 , which can be identical to or different from each other, can be branched or cyclized (C3-C6) aliphatic groups,
    R 2 is (C1-C3) straight chain aliphatic groups, and
    Petition 870200002598, of 01/07/2020, p. 29/39
    [2]
    (2) the molecular weight distribution Mw / Mn is 6-20;
    (2) an organic aluminum component; and (3) dicyclopentyl dimethoxy silane, the weight ratio of component (1) to component (2), based on the ratio of titanium to aluminum, is 1: 10-500, and the weight ratio of the component (2) for component (3) is 10-150: 1; and, in the second stage, tetraethoxy silane is
    Petition 870200002598, of 01/07/2020, p. 31/39
    (2) an organic aluminum component; and (3) the first external electron donor component, the weight ratio of the component (1) to the component (2), based on the ratio of titanium to aluminum, is 1: 10500, and the weight ratio from component (2) to component (3) is 10-150: 1; and
    Petition 870200002598, of 01/07/2020, p. 30/39
    2. Process, according to claim 1, characterized by the fact that:
    in the first stage, the Ziegler-Natta catalyst is composed of the following components:
    2/5 n is 1 or 2, the second external electron donor being shown as the general formula
    R 3 nSi (OR 4 ) 4-n, where n is 0 or 1 or 2;
    R 3 and R 4 , which can be identical to or different from each other, can be (C1-C3) straight chain aliphatic groups; or the second external electron donor is shown as the general formula
    R 5 R6Si (OR7) 2, in which
    R 5 is (C1-C3) straight chain aliphatic groups,
    R6 is branched or cyclized (C3-C6) aliphatic groups, and
    R7 is (C1-C3) linear chain aliphatic groups, and the MFR is measured according to ISO1133 at 230 ° C with a load of 2.16 kg.
    [3]
    (3) the fraction content with a molecular weight greater than 5,000,000 is greater than or equal to 0.8% by weight; and
    3. Process according to claim 1, characterized by the fact that the first external electron donor is dicyclopentyl dimethoxy silane and / or diisopropyl dimethoxy silane.
    3/5 in the second stage, the weight ratio of the organic aluminum component to the second external electron donor component added is 1-50: 1, preferably 2-20: 1
    [4]
    (4) Mz + 1 / Mn is greater than or equal to 70.
    4/5 added in the presence of hydrogen to further propylene homopolymerization, and the amount of tetraethoxy silane is determined according to the amount of the organic aluminum component added in the first stage, so that the weight the proportion of the tetraethoxy silane to organic aluminum is 1: 1-50.
    4. Process according to claim 1, characterized by the fact that the second external electron donor is tetraethoxy silane and / or methyl cyclohexyl dimethoxy silane.
    [5]
    (5) the fraction content with a molecular weight of less than 50,000 is greater than or equal to 17.5% by weight and less than or equal to 30% by weight; and (6) the dispersibility index of the PI polymer is 9.0-16.0.
    5/5 preferably, greater than or equal to 17.5% by weight and less than or equal to 30% by weight.
    5. Process, according to claim 1, characterized by the fact that the said propylene homopolymerization reaction is conducted in two tubular reactors with recycle connected in series.
    [6]
    6. Process, according to claim 1, characterized by the fact that:
    the propylene homopolymerization reaction is in two stages and is carried out in two tubular reactors with recycle connected in series, and in the first stage, the hydrogen content is less than 300 ppmV and the Ziegler-Natta catalyst is composed of the following components:
    [7]
    7. Propylene homopolymer with high melt resistance, characterized by the fact that it is prepared by the process, as defined in any one of claims 1 to 6, and which comprises the following characteristics:
    [8]
    8. Propylene homopolymer with high melt resistance, according to claim 7, characterized by the fact that the fraction content with a molecular weight greater than 5,000,000 is preferably greater than or equal to 1.0% by weight , greater than or equal to 1.5% by weight.
    [9]
    9. Propylene homopolymer with high resistance to fusion, according to claim 7, characterized by the fact that the Mz + 1 / Mn of it is greater than or equal to 80.
    [10]
    10. Propylene homopolymer with high melt resistance, according to claim 7, characterized by the fact that the MFR is 2.5-6g / 10 min at 230 ° C with a load of 2.16 kg.
    [11]
    11. Propylene homopolymer with high melt resistance, according to claim 7, characterized by the fact that the fraction content with a molecular weight less than 50,000 is greater than or equal to 15.0% by weight and less than or equal to to 40% by weight,
    Petition 870200002598, of 01/07/2020, p. 32/39
    [12]
    12. Propylene homopolymer with high melt resistance, according to claim 7, characterized by the fact that the dispersion index of polymer PI is 6.0-20.0.
    [13]
    13. Propylene homopolymer with high melt resistance, according to claim 7, characterized by the fact that it comprises the following characteristics:
    the MFR (1) is 1.6-6g / 10 min, the content (3) is greater than or equal to 1.0% by weight, and the Mz + 1 / Mn is greater than or equal to 80;
    and which comprises the following characteristics:
    [14]
    14. Use of the propylene homopolymer, as defined in any of claims 7 to 13, characterized by the fact that it is in the preparation of foam products, thermoforming products, biaxial elastic films, inflation films and inflation shaped products.
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    同族专利:
    公开号 | 公开日
    CN102884093A|2013-01-16|
    MY158286A|2016-09-30|
    US9068030B2|2015-06-30|
    EP2527376A4|2015-04-29|
    SG182655A1|2012-08-30|
    EP2527376A1|2012-11-28|
    BR112012018282A2|2016-04-19|
    EP2527376B1|2017-07-19|
    US20130023598A1|2013-01-24|
    WO2011088754A1|2011-07-28|
    KR101798500B1|2017-11-16|
    SG10201500468RA|2015-03-30|
    CN102884093B|2014-03-12|
    ZA201206323B|2013-10-30|
    KR20120127466A|2012-11-21|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-07-16| B06T| Formal requirements before examination|
    2019-10-15| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2020-02-18| B09A| Decision: intention to grant|
    2020-04-07| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/01/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    CN2010100009741A|CN102134290B|2010-01-22|2010-01-22|Polypropylene with high melt strength and product thereof|
    CN2010100009756A|CN102134291B|2010-01-22|2010-01-22|Method for preparing polypropylene with high melt strength|
    PCT/CN2011/000107|WO2011088754A1|2010-01-22|2011-01-21|Propylene homopolymer having high melt strength and preparation method thereof|
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