Propylene copolymer, method for producing the same, and use thereof, and polypropylene composition containing the propylene copolymer.

Abstract

The present invention belongs to the field of olefin polymerization and relates to a propylene-based copolymer, its preparation and use, and a polypropylene composition. The propylene-based copolymer may contain 60 to 95% by weight of propylene-derived structural units and 5 to 40% by weight of comonomer-derived structural units, and the propylene-based copolymer has a comonomer dispersity D [PCP] / [C] is 50% to 70%, and the comonomer dispersion degree D [PCP] / [C] = [PCP] / [C] × 100%. When blended with polypropylene, the propylene-based copolymer of the present invention has excellent compatibility with polypropylene, can promote the crystallization of polypropylene, and can improve the mechanical properties of the resulting polypropylene material.

Description

Detailed description of the invention

[0001] [Technical Field] This invention belongs to the field of olefin polymerization. Specifically, this invention relates to propylene copolymers, methods for producing propylene copolymers, uses of propylene copolymers, and polypropylene compositions containing propylene copolymers.

[0002] [Background technology] Propylene copolymers are extremely widely used polyolefin materials. Propylene-α-olefin copolymers with a high comonomer content possess high elasticity and can be used as thermoplastic elastomers for impact resistance modification of polypropylene materials. However, as the comonomer content increases, especially when it reaches 10% by weight or more, the compatibility between propylene copolymers and polypropylene decreases. The incorporation of propylene copolymers hinders the crystallization of polypropylene materials and affects the mechanical properties of the material. Therefore, it is desirable to obtain propylene-α-olefin copolymers with a high comonomer content that can promote the crystallization of polypropylene when incorporated into polypropylene to form a blended material. The crystallization of propylene-α-olefin copolymers is usually related to the degree of dispersion of comonomers in the propylene segment.

[0003] Propylene-α-olefin copolymers with high comonomer content possess high elasticity and low glass transition temperatures, making them suitable for use in low-temperature environments. However, their slow crystallization and high viscosity can lead to pellet adhesion and aggregation during storage and transport. Since propylene copolymers with high comonomer content typically have low initial melting temperatures, adhesion and aggregation problems during storage and transport become particularly pronounced in high-temperature regions, especially during summer. Therefore, developing propylene polymers with high comonomer content and high initial melting temperatures to solve the problems of adhesion and aggregation during storage and transport is an urgent need in this field.

[0004] It is well known that highly crystalline isotactic polypropylene and its copolymers can be produced using chiral bis-indenyl metallocene catalysts. WO2002 / 01745, US2002 / 0004575A1, WO2002 / 083753A1, and US6525157 disclose methods for producing propylene / ethylene copolymers having stereoregularity within the propylene sequence using the chiral metallocene rac-Me2Si(1-indenyl)2HfMe2. US6057408 discloses a method for producing high molecular weight propylene / ethylene copolymers having high crystallinity within the propylene sequence using chiral bis-indenyl metallocene.

[0005] US5767208 and EP0612768 describe ionic catalyst systems based on crosslinked bis-cyclopentadienylhafnium, which can be used to produce high molecular weight ethylene-α-olefin copolymers in high-temperature solution polymerization. Other useful references include CN101124235B, US5455365, US6084115, CN110272515A, and Organometallics 1992,11,2115.

[0006] However, propylene-α-olefin copolymers with high comonomer content produced by prior art still have the aforementioned drawbacks. Therefore, it is desirable in this field to provide a propylene-based copolymer that can eliminate one or more of the above drawbacks.

[0007] [Summary of the Invention] The object of the present invention is to provide a propylene copolymer, a method for producing the same, a method for using the same, and a polypropylene composition containing the propylene copolymer.

[0008] A first aspect of the present invention provides a propylene copolymer, which contains propylene-derived structural units and comonomer-derived structural units, preferably containing 60 to 95% by weight of the propylene-derived structural units and 5 to 40% by weight of the comonomer-derived structural units; the comonomers are ethylene and C4-C 20 It is at least one of α-olefins; and in the propylene copolymer, the degree of comonomer dispersion D [PCP] / [C] The percentage is 50% to 70%, and the comonomer dispersion is D [PCP] / [C] =[PCP] / [C]×100%, where [PCP] is the amount of monodisperse comonomer structural units in the propylene copolymer, and the monodisperse comonomer structural units are comonomer structural units that exist in the form of single comonomer structural units inserted into the propylene segment, and [C] is the total amount of comonomer structural units in the propylene copolymer.

[0009] A second aspect of the present invention provides a method for producing the above-mentioned propylene copolymer, the method being: (A) A step of bringing the main catalyst and co-catalyst into pre-contact to form a homogeneous ionic catalyst solution in a solvent in a pipeline connected to the polymerization reactor, and (B) The homogeneous ionic catalyst solution obtained in step (A) is sent to a polymerization reactor via a pipeline connected to the polymerization reactor, and contacted with a propylene monomer, one or more comonomers, and any hydrogen to carry out olefin polymerization to produce the propylene copolymer.

[0010] According to one embodiment of the present invention, the main catalyst is a metallocene catalyst, preferably at least one of the compounds represented by formula (I), [ka] In formula (I), M is a metal selected from titanium, hafnium, or zirconium. G is carbon, silicon, germanium, tin, or lead. R and R’ are each independently hydrogen, and substituted or unsubstituted C1-C 20 hydrocarbyl, each R’’ is independently a hydrogen atom, a halogen atom, C1-C 20 hydrocarbyl group, C1-C 20 alkoxy group or C6-C 20 aryloxy group, these groups are linear, branched or cyclic, optionally with a halogen atom, C1-C 10 alkyl, C1-C 10 alkoxy, C6-C 10 aryl or C6-C 10 aryloxy substituted, each R’’' is independently a hydrogen atom, C1-C 20 hydrocarbyl group, C1-C 20 alkoxy group or C6-C 20 aryloxy group, and / or The cocatalyst is a boron-containing compound type cocatalyst, an aluminoxane type cocatalyst, or a combination thereof.

[0011] A third aspect of the present invention provides a polymer composition comprising the propylene-based copolymer of the present invention, preferably the polymer composition comprising the propylene-based copolymer of the present invention and at least one other polymer, more preferably the polymer composition comprising polypropylene and the propylene-based copolymer of the present invention, and the polypropylene includes a polypropylene homopolymer, a polypropylene copolymer different from the propylene-based copolymer of the present invention, or a combination thereof.

[0012] A fourth aspect of the present invention provides the use of the propylene-based copolymer of the present invention for the production of a polypropylene composition, and the polypropylene composition comprises polypropylene and a propylene-based copolymer.

[0013] The propylene copolymer of the present invention has a relatively high comonomer content and, at the same time, a specially selected degree of comonomer dispersion. Surprisingly, the inventors have found that by selecting a specific range of comonomer dispersion, a propylene copolymer with desired properties can be obtained. When blended with polypropylene, the propylene copolymer of the present invention exhibits excellent compatibility with polypropylene, can promote the crystallization of polypropylene, and can improve the mechanical properties of the resulting polypropylene material.

[0014] Metallocene catalysts are generally known in the art to have low solubility in aliphatic hydrocarbons and short storage times after dissolution. The present invention's method for producing propylene copolymers allows for the formation of a homogeneous ionic catalyst solution in situ within the pipeline, and the catalyst system exhibits excellent polymerization activity (especially at high temperatures, e.g., above 80°C) and comonomer selectivity, resulting in the production of olefin polymers with higher comonomer content and relatively low, particularly favorable, comonomer dispersibility. Furthermore, in the case of a continuous solution polymerization process, the present invention allows the catalyst to form an active center in situ within the pipeline and be injected into the polymerization reactor in the form of a homogeneous aliphatic solution. This clearly offers superior operability.

[0015] When the terms “one embodiment” or “several embodiments” are used herein, it means that the features, structures, or characteristics described in relation to the embodiments are encompassed in at least one embodiment. In one or more embodiments, these features, structures, or characteristics can be combined in any suitable manner.

[0016] While the individual embodiments described herein can be combined with one another, combinations that violate the laws of nature and combinations that can be excluded by those skilled in the art based on their expertise are not included.

[0017] Various types of ranges are disclosed herein. These ranges include, but are not limited to, ranges of content, ranges of numerical values, ranges of weight ratios, ranges of molar ratios, and so on. When an applicant discloses or claims any type of range, the applicant intends to disclose or claim individually all possible ranges and values ​​that can reasonably be included, such as endpoints of the range, point values ​​within the range and any subranges, and combinations of subranges included therein. Furthermore, when an applicant discloses or claims any type of range and discloses ranges and point values ​​within that range, the range of this application may specifically include ranges formed by combining any endpoint and any point value of a given range, or ranges formed by combining any two point values.

[0018] Except for the examples provided at the end of the “Detailed Description” section, numerical values ​​(such as quantities or conditions) in this specification (including the appended claims) should be understood to be modified in all cases by the term “approximately,” regardless of whether “approximately” actually appears before the numerical value. “Approximately” is intended to allow for a certain degree of slight inaccuracy in the numerical value. Where the inaccuracy provided by “approximately” is not understood in this ordinary sense in the art, “approximately” as used herein refers at least to the variation that may arise from the ordinary methods of measuring and using the parameter. For example, “approximately” may include variations of 5% or less, optionally 4% or less, optionally 3% or less, optionally 2% or less, optionally 1% or less, optionally 0.5% or less, and optionally 0.1% or less.

[0019] Where used herein, unless the context clearly states otherwise, the singular forms “one,” “one kind,” and “the” are intended to include the plural forms as well. The terms “include,” “include,” “contain,” and “have” are inclusive and state the presence of the described features, elements, compositions, processes, integers, operations, and / or components, but do not exclude one or more other features, integers, processes, operations, elements, components, and / or sets thereof. The open term “include” should be understood as a non-restrictive term for claiming various embodiments described herein, although in certain aspects this term should be understood conversely as a restrictive and limiting term such as “consisting of” or “essentially consisting of.”

[0020] Other features and advantages of the present invention are described in detail in the following "Detailed Description".

[0021] [Brief explanation of the drawing] Embodiments of the present invention will be described in detail below with reference to the drawings.

[0022] Figure A1 shows the dynamic mechanical analysis curves of a polypropylene material before and after incorporating the propylene copolymer of Example A4 of the present invention.

[0023] Figure A2 shows the dynamic mechanical analysis curves of the polypropylene material before and after the incorporation of the propylene copolymer of Example A6 of the present invention.

[0024] Figure A3 shows the crystallization temperatures (measured by DSC test) of polypropylene compositions incorporating the propylene copolymers of Examples A1 to A4, which have different ethylene content, as well as the propylene copolymers of Comparative Examples B2 and B3.

[0025] Figures C1 to C3 show the DSC curves of the polypropylene compositions produced in Examples C1 to C3, respectively.

[0026] Figure D shows the dynamic mechanical analysis curves of the homopolymerized polypropylene material before and after the incorporation of the propylene copolymer of Comparative Example B1.

[0027] [Detailed explanation] Specific embodiments of the present invention will be described in detail below. It should be understood that the embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the present invention.

[0028] (Propylene copolymer) The present invention provides a propylene copolymer comprising propylene-derived structural units and comonomer-derived structural units, preferably comprising 60-95% by weight of propylene-derived structural units and 5-40% by weight of comonomer-derived structural units, more preferably comprising 75-93% by weight of propylene-derived structural units and 7-25% by weight of comonomer-derived structural units, wherein the comonomers are ethylene and C4-C 20 At least one of the α-olefins, and in a propylene copolymer, the comonomer dispersion degree D [PCP] / [C] The comonomer dispersion is 50% to 70%, preferably 60% to 70%, for example, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, and 70%. Comonomer dispersion D [PCP] / [C] =[PCP] / [C]×100% (wherein [PCP] is the amount of monodisperse comonomer structural units in the propylene copolymer, monodisperse comonomer structural units are comonomer structural units that exist in the form of single comonomer structural units inserted into propylene segments, and [C] is the total amount of comonomer structural units in the propylene copolymer).

[0029] In the present invention, the weight percentages of propylene-derived structural units and comonomer-derived structural units in a propylene copolymer are based on the total weight of the propylene copolymer.

[0030] According to the present invention, "comonomer dispersibility" represents the degree of dispersion of comonomers in the propylene segment. PCP represents monodisperse comonomer structural units, which exist in the form of propylene monomer structural unit (P) - single comonomer structural unit (C) - propylene monomer structural unit (P), and [PCP] represents the amount of such structural units, and the ratio of [PCP] to the total amount of comonomer structural units is the comonomer dispersibility D [PCP] / [C] That is the case. 13 ¹³C NMR yields the total amount of comonomer structural units [C] and the amount of monodisperse comonomer structural units [PCP]. Here, the "numerical values" for [PCP] and [C] should be measured in the same units, for example, moles (molar content) or weight (weight content).

[0031] Comonomer dispersion degree D [PCP] / [C] teeth, 13 It can be measured by 13C NMR. 13 ¹³C NMR spectroscopy is a well-known method in this art for measuring the amount of comonomers incorporated into a polymer, as well as the linkage of comonomer structural units incorporated into the polymer chain. See, for example, Journal of Macromolecular Science, Reviews in Macromolecular Chemistry and Physics, C29(2&3), 201-317 (1989). The basic method for measuring the comonomer content in olefin copolymers is to use conditions under which the intensity of the peaks corresponding to different carbon atoms in the sample is directly proportional to the total amount of contributing nuclei in the sample. 13 This includes obtaining a 13C NMR spectrum. Methods for ensuring this proportionality are known in the art and include allowing sufficient relaxation time after pulsation, using gate decoupling techniques, and using relaxation agents. 13After obtaining a 13C NMR spectrum and integrating the peaks, the peaks are assigned to correspond to monomeric structural units. Such assignments are known in this art and can be carried out, for example, by referring to known spectra or literature, synthesizing and analyzing model compounds, or using isotope-labeled monomers. The degree of comonomer dispersibility can be determined by the ratio of the peak integral value corresponding to monodisperse comonomer structural units to the peak integral value corresponding to all comonomer structural units in the copolymer.

[0032] In the case of two or more comonomers, the above formula D [PCP] / [C] In the formula =[PCP] / [C]×100%, [PCP] is the total amount of monodisperse comonomer structural units in the propylene copolymer, and [C] is the total amount of all monodisperse comonomer structural units in the propylene copolymer.

[0033] The propylene polymer of the present invention has a high comonomer content. Here, "high comonomer content" means that the comonomer content is 5% by weight or more, based on the total weight of the propylene copolymer. In the present invention, the comonomer content may be 5% to 40% by weight, preferably 7% to 25% by weight, and more preferably 10% to 25% by weight. In the present invention, the comonomer content may be, for example, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight, 25% by weight, 26% by weight, 27% by weight, 28% by weight, 29% by weight, 30% by weight, 31% by weight, 32% by weight, 33% by weight, 34% by weight, 35% by weight, 36% by weight, 37% by weight, 38% by weight, 39% by weight, or 40% by weight.

[0034] The comonomer content can be measured using an infrared spectrophotometer such as the Perkin Elmer PE1760 as follows: The propylene copolymer is pressed into a thin, uniform film at a temperature of approximately 150°C or higher, and then fixed to the infrared spectrophotometer. 600 cm -1 From 4000cm -1 All spectra of the sample up to this point are recorded, and the weight % of the comonomer can be calculated according to the following formula: Comonomer weight % = 82.585 - 111.987x + 30.045x 2 Here, x is 1155cm -1 The peak height was 722 cm. -1 or 732cm -1 This is the ratio to the peak height at the higher of the two locations.

[0035] The comonomer is preferably ethylene, 1-butene, and / or 1-hexene. In the most preferred embodiment, the comonomer is ethylene.

[0036] In embodiments where the comonomer is ethylene, the propylene copolymer of the present invention is a propylene-ethylene copolymer. In the propylene-ethylene copolymer, the degree of dispersion of the ethylene monomer D [PEP] / [E] The dispersion of ethylene monomers is 50% to 70%, preferably 60% to 70%, for example, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, or 70%. [PEP] / [E] =[PEP] / [E]×100% (wherein [PEP] is the amount of monodisperse ethylene monomer structural units in the propylene-ethylene copolymer, where monodisperse ethylene monomer structural units are ethylene monomer structural units that exist in the form of single ethylene monomer structural units inserted into propylene segments, and [E] is the total amount of ethylene monomer structural units in the propylene-ethylene copolymer).

[0037] According to some embodiments, in the propylene-ethylene copolymer of the present invention, the proportion [EEE] / [E] of triple ethylene monomer units is 3.5 to 5%, and / or the proportion [EE] / [E] of double ethylene monomer units is 15 to 20%.

[0038] In some embodiments, the propylene copolymer consists essentially of propylene monomer structural units and ethylene monomer structural units, or consists of propylene monomer structural units and ethylene monomer structural units.

[0039] In some embodiments described herein, ethylene is used as the comonomer; however, these embodiments are equally applicable to propylene copolymers in which other α-olefins are used as comonomers.

[0040] The stereoregularity (mmm stereoregularity) of the triplicate propylene copolymer of the present invention was determined using a nuclear magnetic resonance spectrometer such as Bruker-300, with deuterated chloroform as the solvent, at 110°C. 13 The stereoregularity of the propylene copolymer of the present invention is preferably 75% to 99%, more preferably 80% to 97%.

[0041] The stereoregularity index m / r of the propylene copolymer of the present invention is as described by HNCheng in Macromolecules, Vol. 17, pp. 1950-1955 (1984), 13 The stereochemistry is measured by 13C NMR. The stereochemistry of an adjacent pair of propylene monomer structural units is described by m and r, where m represents meso and r represents racemic. When m / r is 1, it generally represents a syndiotactic polymer, and when m / r is 2, it represents an atactic material. The m / r of the propylene copolymer of the present invention is preferably 3 to 15.

[0042] The density of the propylene copolymer of the present invention is preferably 0.84 to 0.92 g / cc, more preferably 0.85 to 0.89 g / cc. The density is measured at room temperature according to the ASTM D-1505 test method.

[0043] In this specification, "room temperature" refers to approximately 25°C.

[0044] The propylene copolymer of the present invention has a melt flow rate (MFR) of 100 g / 10 min or less, preferably 20 g / 10 min or less, and 0.5 g / 10 min or more, at 190°C under a load of 2.16 kg, which can be measured by the ASTM D-1238 test method.

[0045] In some embodiments, the propylene copolymer of the present invention has a melt index of 0.5 to 50 g / 10 min (190°C, 2.16 kg).

[0046] The blend of the propylene copolymer of the present invention with polypropylene promotes the crystallization of polypropylene. Polypropylene includes polypropylene homopolymers, polypropylene copolymers different from the propylene copolymer of the present invention, or combinations thereof. The polypropylene copolymers different from the propylene copolymer of the present invention comprise 95-100% by weight of propylene-derived structural units and 0-5% by weight of comonomer-derived structural units, each of which is independently ethylene and C4-C4. 20 It is at least one selected from α-olefins.

[0047] Therefore, in a polypropylene composition comprising polypropylene and the propylene copolymer of the present invention, the propylene copolymer can act as a polypropylene crystallization accelerator. Since the propylene copolymer of the present invention can improve the mechanical properties of polypropylene materials, it can also be used as a modifier for polypropylene materials, for example, as a modifier for the mechanical properties of polypropylene materials.

[0048] The propylene copolymer of the present invention exhibits good compatibility with polypropylene materials. The material obtained by blending the propylene copolymer of the present invention with a polypropylene material has only one glass transition temperature, and the crystallization temperature Tc (measured by DSC test) of the blended material is high, indicating that incorporating the propylene copolymer of the present invention can promote the crystallization of polypropylene.

[0049] (Method for producing propylene copolymers) The present invention provides a propylene copolymer, preferably a method for producing the propylene copolymer of the present invention, and the method is (A) A step of bringing the main catalyst and co-catalyst into pre-contact to form a homogeneous ionic catalyst solution in a solvent in a pipeline connected to the polymerization reactor, and (B) The homogeneous ionic catalyst solution obtained in step (A) is sent to a polymerization reactor via a pipeline connected to the polymerization reactor, and contacted with a propylene monomer, one or more comonomers, and any hydrogen to carry out olefin polymerization to produce a propylene copolymer.

[0050] According to some embodiments of the present invention, the main catalyst used in the method of the present invention is a metallocene catalyst. Metallocene catalysts are well known in the art.

[0051] According to some embodiments of the present invention, the main catalyst is at least one of the compounds represented by formula (I), [ka] In formula (I), M is a metal selected from titanium, hafnium, or zirconium; G is carbon, silicon, germanium, tin, or lead; and R and R' are, independently, hydrogen and substituted or unsubstituted C1-C15. 20 Selected from hydrocarbyl atoms; each R'' is independently a hydrogen atom, a halogen atom, C1-C 20 Hydrocarbyl group, C1-C20 Alkoxy group, or C6~C 20 Selected from aryloxy groups, these groups are linear, branched, or cyclic, and optionally contain halogen atoms, C1-C 10 Alkyl, C1-C 10 Alkoxy, C6~C 10 Aryl, or C6~C 10 It is substituted with an aryloxy; each R''' independently represents a hydrogen atom, C1~C 20 Hydrocarbyl group, C1-C 20 Alkoxy group, or C6~C 20 Selected from aryloxy groups; Preferably, R and R' are each independently hydrogen and substituted or unsubstituted C1-C 20 Selected from alkyl groups; each R'' independently consists of a hydrogen atom, a halogen atom, and C1-C2. 12 Alkyl alkyl groups, C1-C 12 Alkoxy group or C6~C 12 Selected from aryloxy groups, these groups are linear, branched, or cyclic, and optionally contain halogen atoms, C1-C 10 Alkyl, C1-C 10 Alkoxy, C6~C 10 Aryl or C6~C 10 Further substituted with aryloxy; each R''' independently represents a hydrogen atom, C1~C 12 Alkyl alkyl groups, C1-C 12 Alkoxy group or C6~C 12 Selected from aryloxy groups; More preferably, R and R' are independently hydrogen and substituted or unsubstituted C1-C 12 Selected from alkyl groups; each R'' independently consists of a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a C6-C6 alkyl group. 12 Selected from aryloxy groups, these groups are linear, branched or cyclic, and optionally contain a halogen atom, C1-C6 alkyl, C1-C6 alkoxy, or C6-C 10 Aryl or C6~C 10It is further substituted with an aryloxy; each R''' independently represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a C6-C6 alkyl group. 12 Selected from aryloxy groups; More preferably, R and R' are independently selected from methyl, ethyl, propyl, butyl, pentyl, or hexyl; each R'' is independently selected from a hydrogen atom, a halogen atom, a C1-C3 alkyl group, a C1-C3 alkoxy group, or a C6-C8 aryloxy group, where these groups are linear, branched, or cyclic and optionally further substituted with a halogen atom, a C1-C3 alkyl group, a C1-C3 alkoxy group, a C6-C8 aryl, or a C6-C8 aryloxy; each R''' is independently selected from a hydrogen atom, a C1-C3 alkyl group, a C1-C3 alkoxy group, or a C6-C8 aryloxy group; More preferably, R and R' are each independently selected from methyl, isopropyl, or tert-butyl; each R'' is independently selected from a hydrogen atom, a halogen atom, methyl, ethyl, or propyl; and each R''' is independently selected from a hydrogen atom, methyl, ethyl, or propyl.

[0052] In formula (I), M is preferably a metal selected from the group consisting of hafnium and zirconium.

[0053] In formula (I), G is preferably silicon.

[0054] In formula (I), the halogen atom is preferably selected from fluorine, chlorine, bromine, iodine, or a combination thereof, and more preferably chlorine.

[0055] According to some embodiments of the present invention, the co-catalyst is a boron-containing compound type co-catalyst or an aluminoxane type co-catalyst. Preferably, the co-catalyst is a boron-containing compound type co-catalyst.

[0056] According to some embodiments of the present invention, the boron-containing compound type co-catalyst comprises a structure represented by formula (II), (Z)4B - (II) In formula (II), Z is an optionally substituted phenyl derivative, and any substituent is a C1-C6 haloalkyl or halogen group. Boron-containing compound type co-catalysts containing the structure represented by formula (II) are known in the art. Preferably, the boron-containing compound type co-catalyst is selected from the group consisting of triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylbenzylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylphenylammonium tetrakis(pentafluorophenyl)borate, and mixtures thereof.

[0057] According to some embodiments of the present invention, the co-catalyst may be an aluminoxane type co-catalyst, for example, an alkylaluminoxane type co-catalyst such as methylaluminoxane. The aluminoxane type co-catalyst is preferably a modified alkylaluminoxane type co-catalyst soluble in alkane solvents, for example, modified methylaluminoxane (such as Nouryon MMAO-3A and MMAO-7, or a custom-made product soluble in alkane solvents such as hexane and heptane).

[0058] According to the present invention, "pre-contacting the main catalyst and the co-catalyst" can be relatively flexible. In one embodiment, "pre-contacting the main catalyst and the co-catalyst" means mixing a main catalyst mixture, which is a mixture of the main catalyst and a solvent, with a co-catalyst mixture, which is a mixture of the co-catalyst and a solvent. That is, first, the main catalyst and the co-catalyst are each mixed with a solvent, and then, for example, they are mixed together at a predetermined flow rate.

[0059] According to the present invention, the expression "forming a homogeneous ionic catalyst solution in situ in a pipeline connected to a polymerization reactor" means that the main catalyst mixture and the co-catalyst mixture are directly combined in the pipeline to form an ionic catalyst in the pipeline connected to the polymerization reactor, and then enter the polymerization reactor to initiate the reaction. According to some embodiments, one or both of the main catalyst mixture and the co-catalyst mixture may be mixed via a mixer before being sent to the pipeline. According to some preferred embodiments of the present invention, the main catalyst mixture and the co-catalyst mixture are directly combined in the pipeline to form an ionic catalyst in the pipeline connected to the polymerization reactor, and then enter the polymerization reactor to initiate the reaction.

[0060] "A homogeneous ionic catalyst solution formed in situ within the pipeline" means that, when observed with the naked eye, the solution is homogeneous without any apparent particle precipitation, and no solid particles settle after being left standing for 30 minutes.

[0061] According to a preferred embodiment of the present invention, in order to obtain the propylene copolymer of this application, the length L of the pipeline through which the main catalyst and co-catalyst pass from the start of pre-contact to entering the polymerization reactor is 30 × W / d 2 ≤L ≤ 1000 × W / d 2 (L is in meters; W is the total flow rate of the main catalyst, co-catalyst, and solvent (usually the sum of the flow rates of the main catalyst mixture and the co-catalyst mixture), in kg / h; and d is the inner diameter of the pipeline, in millimeters.) It should be controlled to satisfy this condition. According to some embodiments, preferably, L is given by the following formula: 30 × W / d 2 ≤L ≤ 900 × W / d 2 ;30×W / d 2 ≤L ≤ 850 × W / d 2 ;30×W / d 2 ≤L ≤ 800 × W / d 2 ;30×W / d 2 ≤L ≤ 750 × W / d 2 ;30×W / d 2 ≤L ≤ 700 × W / d2 ; 30 × W / d 2 ≤ L ≤ 650 × W / d 2 ; 30 × W / d 2 ≤ L ≤ 600 × W / d 2 ; 30 × W / d 2 ≤ L ≤ 550 × W / d 2 ; 30 × W / d 2 ≤ L ≤ 500 × W / d 2 ; 30 × W / d 2 ≤ L ≤ 450 × W / d 2 ; 30 × W / d 2 ≤ L ≤ 400 × W / d 2 ; 30 × W / d 2 ≤ L ≤ 350 × W / d 2 ; 30 × W / d 2 ≤ L ≤ 300 × W / d 2 ; 30 × W / d 2 ≤ L ≤ 250 × W / d 2 ; 30 × W / d 2 ≤ L ≤ 200 × W / d 2 ; or 30 × W / d 2 ≤ L ≤ 150 × W / d 2 is satisfied. According to some embodiments, preferably, L is the following formula: 40 × W / d 2 ≤ L ≤ 1000 × W / d 2 ; 40 × W / d 2 ≤ L ≤ 900 × W / d 2 ; 40 × W / d 2 ≤ L ≤ 850 × W / d 2 ; 40 × W / d 2 ≤ L ≤ 800 × W / d 2 ; 40 × W / d 2 ≤ L ≤ 750 × W / d 2 ; 40 × W / d 2 ≤ L ≤ 700 × W / d 2 ; 40 × W / d 2 ≤ L ≤ 650 × W / d 2 ; 40 × W / d 2 ≤ L ≤ 600 × W / d 2 ; 40 × W / d 2 ≤ L ≤ 550 × W / d 2 ; 40 × W / d 2 ≤ L ≤ 500 × W / d 2 ; 40 × W / d 2 ≤ L ≤ 450 × W / d 2 ; 40 × W / d2 ≤L ≤ 400 × W / d 2 ;40×W / d 2 ≤L ≤ 350 × W / d 2 ;40×W / d 2 ≤L ≤ 300 × W / d 2 ;40×W / d 2 ≤L ≤ 250 × W / d 2 ;40×W / d 2 ≤L ≤ 200 × W / d 2 ; or 40 × W / d 2 ≤L ≤ 150 × W / d 2 The following conditions are met. According to some embodiments, preferably, L is given by the following formula: 50 × W / d 2 ≤L ≤ 1000 × W / d 2 , 50×W / d 2 ≤L ≤ 900 × W / d 2 , 50×W / d 2 ≤L ≤ 850 × W / d 2 , 50×W / d 2 ≤L ≤ 800 × W / d 2 , 50×W / d 2 ≤L ≤ 750 × W / d 2 , 50×W / d 2 ≤L ≤ 700 × W / d 2 , 50×W / d 2 ≤L ≤ 650 × W / d 2 , 50×W / d 2 ≤L ≤ 600 × W / d 2 , 50×W / d 2 ≤L ≤ 550 × W / d 2 , 50×W / d 2 ≤L ≤ 500 × W / d 2 , 50×W / d 2 ≤L ≤ 450 × W / d 2 , 50×W / d 2 ≤L ≤ 400 × W / d 2 , 50×W / d 2 ≤L ≤ 350 × W / d 2 , 50×W / d 2 ≤L ≤ 300 × W / d 2 , 50×W / d 2 ≤L ≤ 250 × W / d 2 , 50×W / d 2 ≤L ≤ 200 × W / d 2 , or 50 × W / d 2≤L ≤ 150 × W / d 2 Satisfying the following conditions. More preferably, L is given by the following formula: 40 × W / d 2 ≤L ≤ 900 × W / d 2 It can satisfy the following equation, and more preferably, L is given by: 50 × W / d 2 ≤L ≤ 800 × W / d 2 This can be satisfied. Specifically, L is 30 × W / d 2 , 35×W / d 2 , 40×W / d 2 , 45×W / d 2 , 50×W / d 2 , 60×W / d 2 , 70×W / d 2 , 80×W / d 2 , 90×W / d 2 , 100 × W / d 2 , 150×W / d 2 , 200 × W / d 2 , 250×W / d 2 , 300×W / d 2 , 350×W / d 2 , 400×W / d 2 , 450×W / d 2 , 500×W / d 2 , 550×W / d 2 , 600×W / d 2 , 650×W / d 2 , 700×W / d 2 , 750×W / d 2 , 800×W / d 2 , 850×W / d 2 , 900×W / d 2 , 950×W / d 2 Or 1000 × W / d 2It can be that the range of L is defined between any two of the aforementioned values, where the unit of L is m, W is the total flow rate of the main catalyst, co-catalyst and solvent, the unit of which is kg / h, and d is the inner diameter of the pipeline, the unit of which is mm. Surprisingly, the inventors of this application have found that when the above conditions are met, the main catalyst and the co-catalyst can be well pre-contacted, and a homogeneous ionic catalyst solution with superior catalytic performance can be obtained. After the obtained homogeneous ionic catalyst solution is placed in a reactor, the propylene copolymer of this application, in particular a propylene copolymer having the preferred properties (especially comonomer dispersibility) as defined in this application can be produced.

[0062] In this invention, when the flow rates of the main catalyst mixture and the co-catalyst mixture are measured by volume, the volume flow rate can be converted to a mass flow rate using the density of the solvent. For example, the density of n-hexane is 0.66 g / cm³. 3 Therefore, when using n-hexane as the solvent to obtain a main catalyst mixture and a co-catalyst mixture, the density of n-hexane can be used to convert the volumetric flow rate to a mass flow rate and apply it to the above formula.

[0063] According to embodiments of the present invention, the solvent used for preliminary contact is preferably C4-C 20 The hydrocarbon is at least one of linear, branched, or cyclic aliphatic hydrocarbons, specifically preferably at least one of n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, cyclopentane, and cyclohexane; more preferably at least one of n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, cyclopentane, and cyclohexane; even more preferably at least one of n-pentane, isopentane, n-hexane, isohexane, and cyclohexane; and even more preferably n-hexane.

[0064] According to some embodiments of the present invention, a main catalyst mixture can be obtained by mixing the main catalyst and a solvent. The solvent is C4-C 20 It is at least one of a linear, branched, or cyclic aliphatic hydrocarbon, preferably at least one of n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, cyclopentane, and cyclohexane; more preferably at least one of n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, cyclopentane, and cyclohexane; even more preferably at least one of n-pentane, isopentane, n-hexane, isohexane, and cyclohexane; and even more preferably n-hexane.

[0065] The concentration of the main catalyst mixture can be appropriately determined by those skilled in the art. For example, the concentration of the main catalyst mixture can be 0.001 μmol / mL to 1000 μmol / mL, preferably 0.01 μmol / mL to 100 μmol / mL. For example, the concentration of the main catalyst mixture can be 0.1 μmol / mL.

[0066] According to some embodiments of the present invention, a co-catalyst mixture can be obtained by mixing the co-catalyst and the solvent. The solvent is C4-C 20 It is at least one of a linear, branched, or cyclic aliphatic hydrocarbon, preferably at least one of n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, cyclopentane, and cyclohexane; more preferably at least one of n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, cyclopentane, and cyclohexane; even more preferably at least one of n-pentane, isopentane, n-hexane, isohexane, and cyclohexane; and even more preferably n-hexane.

[0067] The concentration of the co-catalyst mixture can be appropriately determined by those skilled in the art. For example, the concentration of the co-catalyst mixture can be 0.001 μmol / mL to 1000 μmol / mL, preferably 0.01 μmol / mL to 100 μmol / mL. For example, the concentration of the co-catalyst mixture can be 0.15 μmol / mL.

[0068] According to some embodiments of this application, the solvent of the main catalyst mixture is the same as the solvent of the co-catalyst mixture. Preferably, the solvent of the main catalyst mixture is the same as the solvent of the co-catalyst mixture, and the solvent is C4-C 20 At least one of linear, branched, or cyclic aliphatic hydrocarbons, preferably at least one of n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, cyclopentane, and cyclohexane; more preferably at least one of n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, cyclopentane, and cyclohexane; even more preferably at least one of n-pentane, isopentane, n-hexane, isohexane, and cyclohexane; and even more preferably n-hexane.

[0069] According to a preferred embodiment of the present invention, the method for producing the propylene copolymer of the present invention is: (A) A step of pre-contacting the main catalyst mixture and the co-catalyst mixture in a pipeline connected to the polymerization reactor to form a homogeneous ionic catalyst solution in the solvent in situ, and (B) The homogeneous ionic catalyst solution obtained in step (A) is sent to a polymerization reactor via a pipeline connected to the polymerization reactor, and contacted with a propylene monomer, one or more comonomers, and any hydrogen to carry out olefin polymerization to produce a propylene copolymer.

[0070] The manufacturing method of the present invention may further include a step of preparing a main catalyst mixture and a co-catalyst mixture before step (A). According to some embodiments, preparing the main catalyst mixture involves mixing the main catalyst with a solvent and stirring as necessary. According to some embodiments, preparing the co-catalyst mixture involves mixing the co-catalyst with a solvent and stirring as necessary. Stirring can be carried out using various stirring devices known in the art.

[0071] Conventional techniques generally require the use of aromatic solvents, such as toluene, to improve the solubility of catalysts, particularly metallocene catalysts containing bis-indenyl ligands. However, aromatic solvents have high boiling points and are difficult to remove from polymers. When aromatic solvents are introduced during polymerization processes, such as solution polymerization, the resulting polymers contain aromatic substances. The presence of aromatic substances in polymers negatively impacts their applications, for example, making them unsuitable for use in the food and medical fields.

[0072] According to some embodiments of the present invention, aromatic hydrocarbon compounds are not used in the process for producing the propylene copolymer of the present invention. For example, by using an aliphatic solvent in the method of the present invention, the use of aromatic solvents is eliminated. Therefore, the weight content of aromatic hydrocarbon compounds in the propylene copolymer obtained by the production method of the present invention, for example, the propylene copolymer of the present invention, is less than 500 ppm, preferably less than 300 ppm, more preferably less than 200 ppm or less than 100 ppm, more preferably less than 50 ppm, and most preferably no aromatic hydrocarbon compounds are present. The expression "aromatic hydrocarbon compounds are not used" means that aromatic hydrocarbon compounds are intentionally not used in the method of the present invention. According to some embodiments, aromatic hydrocarbon compounds include those known in the art, such as benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, halogenated derivatives thereof, and mixtures thereof.

[0073] In the method of the present invention, the amounts of co-catalyst and main catalyst used may be those conventionally used in the art. Those skilled in the art can select the amounts of co-catalyst and main catalyst used. Preferably, the molar ratio of co-catalyst to central metal atoms M in the main catalyst is 0.5:1 to 5:1, more preferably 1:1 to 2:1.

[0074] According to the present invention, in some embodiments, alkylaluminum can be added to an olefin polymerization system. The timing of the addition of alkylaluminum may be relatively flexible, and it can be added to the pipeline or to the polymerization reactor, preferably to the pipeline. According to some embodiments, the aluminum alkyl is added after the start of pre-contact. According to some preferred embodiments, the alkylaluminum is added downstream of the pre-contact point (i.e., closer to the polymerization reactor) to the pre-contact pipeline connected to the polymerization reactor.

[0075] The alkylaluminum used in the present invention may be one that has been conventionally used in the art. In some embodiments, the alkylaluminum may have a structure represented by formula (III); AlR3(III) In equation (III), R is C1 to C 12 Hydrocarbyl, preferably C1-C 12 It is alkyl, more preferably C1-C8 alkyl.

[0076] More specifically, the alkylaluminum may be at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, and triisooctylaluminum.

[0077] According to some embodiments of the present invention, alkylaluminum is added in the form of an alkylaluminum solution. According to some preferred embodiments, the solvent of the alkylaluminum solution is C4-C 20The alkylaluminum is a linear, branched, or cyclic aliphatic hydrocarbon, and preferably the solvent of the alkylaluminum solution is the same as the solvent used for the preliminary contact (i.e., the solvent used to produce the main catalyst mixture and the co-catalyst mixture). The concentration of the alkylaluminum solution can vary over a wide range and can be appropriately selected by those skilled in the art, for example, it can be 1 to 20 mol / L.

[0078] According to some embodiments, both boron-containing compound type co-catalysts and alkylaluminum are used in the method of the present invention.

[0079] The olefin polymerization method in this invention may be bulk homogeneous polymerization, supercritical polymerization, solution polymerization, or near-critical dispersion polymerization. These polymerization methods are known in the art.

[0080] According to a preferred embodiment, the polymerization method of the present invention is solution polymerization.

[0081] Solution polymerization must be carried out in the presence of at least one polymerization solvent. According to some embodiments, the polymerization solvent is C3-C 10 Alkanes and / or monocyclic aromatic hydrocarbons, preferably C3-C3 10 It could be an alkane (C3~C) 10 The alkane is preferably at least one of propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, cyclopentane, and cyclohexane; the monocyclic aromatic hydrocarbon is preferably toluene and / or xylene. Preferably the polymerization solvent is at least one of n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, cyclopentane, and cyclohexane; more preferably at least one of n-pentane, isopentane, n-hexane, isohexane, and cyclohexane; even more preferably n-hexane.

[0082] According to some preferred embodiments, the polymerization method of the present invention is solution polymerization, and the solvent used in the solution polymerization is the same as the solvent used to produce the main catalyst mixture and / or co-catalyst mixture. According to some preferred embodiments, the solvent used in the solution polymerization, the solvent used to produce the main catalyst mixture, and the solvent used to produce the co-catalyst mixture are all the same, and preferably the solvent is C4-C 20 It is at least one of linear, branched, or cyclic aliphatic hydrocarbons; preferably at least one of n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, cyclopentane, and cyclohexane; more preferably at least one of n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, cyclopentane, and cyclohexane; even more preferably at least one of n-pentane, isopentane, n-hexane, isohexane, and cyclohexane; and even more preferably n-hexane.

[0083] According to a preferred embodiment of the present invention, the solvent used for solution polymerization is the same as the solvent used for preliminary contact. According to a preferred embodiment of the present invention, when alkylaluminum is used, the solvent for the alkylaluminum solution, the solvent used for solution polymerization, and the solvent used for preliminary contact are all the same.

[0084] The polymerization of the present invention may be continuous, semi-continuous, or batch operation. These modes of operation are known in the art. The polymerization of the present invention is preferably continuous polymerization.

[0085] The olefin polymerization of the present invention can be carried out using conventional process conditions in the art. Those skilled in the art can select appropriate polymerization conditions according to the polymerization process used, and these polymerization conditions are known in the art.

[0086] According to some embodiments, the polymerization temperature for olefin polymerization in the present invention is 60 to 150°C, and the polymerization pressure is 0.1 to 10 MPa.

[0087] In the manufacturing method of the present invention, once polymerization is complete, the polymerization can be terminated and post-processing can be performed to obtain the polymer. Termination of polymerization reactions and post-processing are known in the art.

[0088] (Composition containing a propylene copolymer) The present invention provides a polymer composition comprising the propylene copolymer of the present invention, preferably comprising the propylene copolymer of the present invention and at least one additional polymer, the additional polymer being different from the propylene copolymer of the present invention.

[0089] According to some embodiments of the present invention, the polymer composition is a polypropylene composition comprising the propylene copolymer of the present invention and polypropylene. Polypropylene includes polypropylene homopolymers, polypropylene copolymers different from the propylene copolymer of the present invention, or combinations thereof.

[0090] According to some embodiments of the present invention, the present invention provides a polypropylene composition, and the polypropylene composition: (1) 30 to 99.5% by weight of the propylene copolymer of the present invention (first polymer component), and (2) A second polymer component (polypropylene) in an amount of 0.5 to 70% by weight, comprising a second polymer component containing 95 to 100% by weight of propylene-derived structural units and 0 to 5% by weight of comonomer-derived structural units, Any comonomer in the second polymer component is independently ethylene and C4-C4. 20 Selected from at least one of the α-olefins.

[0091] According to some embodiments, the initial melting temperature of the polypropylene composition is 80°C or higher, preferably 90°C or higher, and the enthalpy of fusion is less than 50 J / g, preferably less than 40 J / g.

[0092] Both the initial melting temperature and the enthalpy of melting are measured by DSC.

[0093] In the present invention, the content of the propylene copolymer of the present invention and the content of the second polymer component in the polypropylene composition are calculated based on the total weight of the polypropylene composition.

[0094] According to a preferred embodiment of the present invention, in the polypropylene composition, the content of the propylene copolymer of the present invention is 50 to 99% by weight, and the content of the second polymer component is 1 to 50% by weight, preferably the content of the propylene copolymer of the present invention is 60 to 95% by weight, and the content of the second polymer component is 5 to 40% by weight.

[0095] According to the present invention, preferably, in the polypropylene composition, the second polymer component satisfies a certain degree of comonomer dispersion. Specifically, the degree of dispersion D in the propylene segment of the comonomer-derived structural units contained in the second polymer component. [PCP] / [C] The variance is 50% to 75%, for example, 55%, 60%, 65%, and 70%, with a variance of D. [PCP] / [C] As described above, in some preferred embodiments of the present invention, the second polymer component can be produced by the polymerization method of the present invention.

[0096] According to the present invention, one or both of the propylene copolymer and the second polymer component of the present invention further have at least one of the following features: The mmm stereoregularity is in the range of 75-99%, preferably 80-97%; The stereoregularity index m / r is between 3 and 20.

[0097] The polypropylene composition of the present invention has a relatively low glass transition temperature. According to some embodiments of the present invention, the polypropylene composition of the present invention has a glass transition temperature of -29°C or lower, preferably -30°C or lower. The glass transition temperature can be measured by DSC.

[0098] The polypropylene composition of the present invention contains the two polymer components mentioned above, but has only one melting peak in the DSC curve. The polypropylene composition of the present invention can be characterized by its melting point (Tm). The melting point can be measured by differential scanning calorimetry (DSC).

[0099] The general procedure for DSC is as follows: A 10 mg sample is placed in a crucible and measured with a differential scanning calorimeter (e.g., METTLER DSC1). Under a nitrogen atmosphere, the temperature is increased from -70°C to 200°C at a heating rate of 10°C / min and maintained for 1 minute, then the temperature is decreased to -70°C at a rate of 10°C / min and maintained for 3 minutes, and then the temperature is increased to 200°C at a rate of 10°C / min. The data from the second temperature scan is recorded. For the purposes of this application, the maximum value of the highest temperature peak is considered to be the melting point of the polymer. In this application, a “peak” is defined as the point at which the overall gradient of the DSC curve (heat flow vs. temperature) changes from positive to negative and forms a maximum value without shifting relative to the baseline, and the DSC curve is plotted to show a positive peak at the end of the exothermic reaction.

[0100] The melting point Tm (measured by DSC) of the polypropylene composition may be higher than 100°C and lower than 140°C, preferably lower than 130°C, and more preferably lower than 120°C.

[0101] The polypropylene composition of the present invention can be characterized by its enthalpy of fusion (ΔHm). The enthalpy of fusion can be measured by DSC. The polypropylene composition of the present invention has an enthalpy of fusion of 0.5 to 50 J / g, preferably 5 to 40 J / g, more preferably 10 to 30 J / g, and most preferably 15 to 25 J / g.

[0102] The degree of crystallinity of the polypropylene composition of the present invention can be determined by dividing the ΔHm of the sample by the ΔHm of a 100% crystalline polymer. In the case of isotactic polypropylene, the ΔHm of a 100% crystalline polymer is assumed to be 189 J / g. The degree of crystallinity of the polypropylene composition of the present invention may be less than 20%, preferably less than 15%, and more preferably 5-12%.

[0103] The density of the polypropylene composition of the present invention is preferably 0.84 to 0.92 g / cc, and more preferably 0.86 to 0.89 g / cc, as measured at room temperature using the test method ASTMD-1505.

[0104] The melt flow rate (MFR) of the polypropylene composition of the present invention is 100 g / 10 min or less, preferably 20 g / 10 min or less, under a load of 2.16 kg at 190°C, and is measured by test method ASTM D-1238.

[0105] According to the present invention, a polypropylene composition can be obtained by mixing the propylene copolymer of the present invention with a second polymer component in a molten or solution state. These mixing modes are known in the art and can be appropriately selected and used by those skilled in the art.

[0106] The polypropylene composition of the present invention has a high comonomer content and a relatively high initial melting temperature, and therefore can avoid problems of adhesion and aggregation during storage and transport.

[0107] The propylene composition of the present invention, when blended with polypropylene, promotes the crystallization of polypropylene. Therefore, in a polypropylene material comprising polypropylene and the polypropylene composition, the polypropylene composition can act as a polypropylene crystallization accelerator. Furthermore, since it can improve the mechanical properties of the polypropylene material, the polypropylene composition can also be used as a modifier for the polypropylene material, specifically as a modifier of the mechanical properties of the polypropylene material.

[0108] The present invention also provides the use of a polypropylene composition for manufacturing a polypropylene material, the polypropylene material comprising polypropylene and a polypropylene composition.

[0109] The present invention also provides a polypropylene material comprising polypropylene and the above-mentioned polypropylene composition.

[0110] The polypropylene composition and / or polypropylene material of the present invention may contain additives known in the art, such as fillers, antioxidants, surfactants, plasticizers, antiblocking agents, pigments, dyes, processing aids, UV stabilizers, lubricants, waxes, and nucleating agents. The additives may be present in typical effective amounts known in the art, for example, 0.001% to 10% by weight. Those skilled in the art can select and use these additives in an appropriate manner.

[0111] [Examples] The present invention will be further described below with reference to examples, but the scope of the present invention is not limited to these examples.

[0112] In the following examples, the evaluation and test methods are as follows: 1. The melt flow rate (190°C / 2.16 kg) was measured according to the method of ASTM-D 1238.

[0113] 2. Ethylene monomer structural unit content in propylene copolymers: Measured as follows using an infrared spectrophotometer Perkin Elmer PE1760: The propylene copolymer was pressed into a thin, uniform film at a temperature of approximately 150°C or higher, and then fixed to the infrared spectrophotometer. 600 cm -1 From 4000cm -1 All spectra of the samples up to a certain point were recorded, and the weight percentage of ethylene monomer structural units was calculated according to the following formula: Ethylene weight % = 82.585 - 111.987x + 30.045x 2 Here, x is 1155cm -1The peak height was 722 cm. -1 or 732cm -1 This is the ratio to the peak height at the higher of the two locations.

[0114] 3. Ethylene dispersion: D [PEP] / [E] =[PEP] / [E]×100% (wherein [PEP] is the amount of monodisperse ethylene monomer structural units in the propylene-ethylene copolymer, and monodisperse ethylene monomer structural units are ethylene monomer structural units that exist in the form of single ethylene monomer structural units inserted into propylene segments, and [E] is the total amount of ethylene monomer structural units in the propylene copolymer, and the total amount of ethylene monomer structural units [E] and the amount of monodisperse ethylene monomer structural units [PEP] are equal to 100% 13 The measurement was performed by 13C NMR.

[0115] 4. Density was measured at room temperature according to the ASTM-D792 method.

[0116] 5. Nuclear magnetic hydrogen and nuclear magnetic carbon spectra were measured at 110°C using a Bruker-300 nuclear magnetic resonance spectrometer with deuterated chloroform as the solvent.

[0117] 6. The mmm stereoregularity is, 13 Measured by 13C NMR; see the method disclosed in U.S. Patent US7232871.

[0118] 7. The stereochemical regularity index m / r is, 13 The measurement was performed by 13C NMR; for detailed methods, please refer to the description in HNCheng, Macromolecules, Vol. 17, pp. 1950-1955 (1984).

[0119] 8. The melting point was measured by differential scanning calorimetry (DSC). The general method for DSC was as follows: A 10 mg sample was placed in a crucible and measured using a METTLER DSC1 differential scanning calorimetry instrument. Under a nitrogen atmosphere, the temperature was increased from -70°C to 200°C at a heating rate of 10°C / min, maintained for 1 minute, then cooled down to -70°C at 10°C / min, maintained for 3 minutes, and then increased to 200°C at 10°C / min. The data from the second heating scan was recorded. The maximum value of the highest temperature peak was considered to be the melting point of the polymer.

[0120] 9. Polymerization activity: After drying the polymer obtained by polymerization, its weight was measured and divided by the amount of catalyst added during polymerization to obtain the catalytic activity.

[0121] 10. The enthalpy of melting was measured by DSC as described above.

[0122] [Examples A1-A4] The polymerization reaction was carried out continuously in a 1.8 L polymerization vessel. The polymerization vessel was equipped with a mechanical stirrer. The temperature of the polymerization vessel could be controlled by controlling the jacket temperature via an oil bath. The temperature inside the reactor was set to 90°C. The polymerization vessel was connected to a propylene pipeline, an ethylene pipeline, an n-hexane pipeline, and a catalyst injection pipeline. The solvent and monomer feeds entering the reactor were measured by a mass flow controller. The hydrogen feed was incorporated into the ethylene pipeline after passing through a mass flow controller. The material flow rate and pressure were controlled by a variable-speed diaphragm pump.

[0123] Dimethylsilylbis(5,6,7,8-tetrahydro-2,5,5,8,8-pentamethylbenzindenyl)dimethylhafnium was used as the main catalyst. For its synthesis method, please refer to U.S. Patent 60 / 586465. The main catalyst was mixed with n-hexane solvent, and the resulting main catalyst mixture had a concentration of 0.1 μmol / mL. The boron-containing compound was the commercially available compound triphenylcarbeniumtetrakis(pentafluorophenyl)borate, which was mixed with n-hexane solvent. The resulting boron-containing compound mixture had a concentration of 0.15 μmol / mL. The main catalyst mixture, the boron-containing compound mixture, and triisobutylaluminum solution (n-hexane solution at a concentration of 1 mmol / mL) were measured using a pump and a mass flow meter. After mixing the main catalyst mixture and the boron-containing compound mixture in a pipeline, the mixture was introduced into the reactor via a pipeline 0.2 m long with an inner diameter of 4.5 mm. Next, the triisobutylaluminum solution was added to the pipeline at a distance of 0.1 m from the reactor.

[0124] The reactor was operated at 30 bar with stirring. A discharge pipeline was located at the bottom of the polymerization vessel. Water was added to the discharge pipeline along with the stabilizer tri(2,4-di-tert-butylphenyl) phosphite to stop the polymerization reaction. The product was then heated in a heat exchanger and fed into a defoliation unit. Polymer pellets were obtained using an extruder and an underwater pelletizer.

[0125] The specific process conditions and results are shown in Table A1. [Table 1]

[0126] [Examples A5-A6] The polymerization procedure of Example A1 was used, except that the main catalyst mixture and co-catalyst mixture were measured using a pump and mass flow meter, mixed in a pipeline, and then introduced into the reactor via a pipeline 2 m long with an inner diameter of 4.5 mm.

[0127] The specific process conditions and results are shown in Table A2. [Table 2]

[0128] [Examples A7-A9] The polymerization procedure of Example A1 was used, except that the main catalyst was dimethylsilylbis(5,6,7,8-tetrahydro-2,5,5,8,8-pentamethylbenzindenyl)zirconium dichloride. For its synthesis method, please refer to U.S. Patent US60 / 586465. The co-catalyst was MMAO-3A, ​​purchased from Nouryon Company. The main catalyst mixture and co-catalyst mixture were measured using a pump and mass flow meter, mixed in a pipeline, and then introduced into the reactor via a 0.5 m long, 4.5 mm inner diameter pipeline.

[0129] The specific process conditions and results are shown in Table A3. [Table 3]

[0130] [Test Example A] Blend tests were conducted by incorporating the propylene copolymers of Examples A1-A9 into homopolymerized polypropylene (PP; Sinopec PPH-M16). The weight ratio of propylene copolymer to PP was 13:87. The dynamic mechanical analysis curve (DMA curve) of the blend was measured using an RSA III DMA dynamic thermomechanical analyzer. The glass transition temperature (Tg) of the blend is the temperature of the tan delta peak. Solid-state testing was performed in dynamic mode using a torsion clamp in a liquid nitrogen environment. A heating rate of 3°C / min, a frequency of 1 rad / sec, and an initial strain of 0.1% were used. The average sample size was 45.0 mm × 12.6 mm × 3.2 mm. The compatibility between the propylene copolymer and the PP material can be reflected by the Tg peak in the DMA curve. Each material obtained after blending had only one glass transition temperature peak in the DMA curve, and the crystallization temperature Tc (obtained by DSC test) of the PP material was higher. This demonstrates that the incorporation of the propylene copolymer of the present invention can promote the crystallization of PP.

[0131] Figure A1 shows the dynamic mechanical analysis curves of the polypropylene material before and after the incorporation of the propylene copolymer of Example A4 of the present invention. The curve with a lower peak temperature represents the polypropylene material after the incorporation of the sample from Example A4. From Figure A1, it can be seen that the material obtained after blending the propylene copolymer of the present invention with PP had only one glass transition temperature peak.

[0132] Figure A2 shows the dynamic mechanical analysis curves of the polypropylene material before and after the incorporation of the propylene copolymer of Example A6 of the present invention. The curve with a lower peak temperature represents the polypropylene material after the incorporation of the sample from Example A6. From Figure A2, it can be seen that the material obtained after blending the propylene copolymer of the present invention with PP had only one glass transition temperature peak.

[0133] Figure A3 shows the crystallization temperatures of the propylene copolymers of Examples A1-A4 and the polypropylene compositions incorporating the propylene copolymers of Comparative Examples B2 and B3, where the weight ratio of propylene copolymer to polypropylene was 13:87. Figure A3 shows that after incorporating the propylene copolymer of the present invention, the crystallization temperature Tc (obtained by DSC test) of the polypropylene composition increased, indicating that the incorporation of the propylene copolymer of the present invention can promote the crystallization of polypropylene. For Comparative Examples B2 and B3, after blending with polypropylene in a weight ratio of 13:87, the crystallization temperatures of the polypropylene compositions were 117.9°C and 117.8°C, respectively.

[0134] [Examples B1-B4] (Polymerization procedure) The continuous polymerization reaction was carried out in a 1.8 L polymerization vessel. The polymerization vessel was equipped with a mechanical stirrer. The temperature of the polymerization vessel could be controlled by controlling the jacket temperature via an oil bath. The polymerization vessel was connected to a propylene pipeline, an ethylene pipeline, an n-hexane pipeline, and a catalyst injection pipeline. The solvent and monomer feeds entering the reactor were measured by a mass flow controller. The material flow rate and pressure were controlled by a variable-speed diaphragm pump. The hydrogen feed was incorporated into the ethylene pipeline after passing through a mass flow controller.

[0135] The main catalyst was dimethylsilylbis(5,6,7,8-tetrahydro-2,5,5,8,8-pentamethylbenzindenyl)dimethylhafnium. For its synthesis method, please refer to U.S. Patent US60 / 586465. The main catalyst was mixed with n-hexane solvent, and the resulting main catalyst mixture had a concentration of 0.1 μmol / mL. The boron-containing compound was the commercially available compound triphenylcarbeniumtetrakis(pentafluorophenyl)borate, and this boron-containing compound was mixed with n-hexane solvent. The resulting boron-containing compound mixture had a concentration of 0.15 μmol / mL. The main catalyst mixture, the boron-containing compound mixture, and triisobutylaluminum solution (n-hexane solution at a concentration of 1 mmol / mL) were measured using a pump and a mass flow meter. After mixing the main catalyst mixture and the boron-containing compound mixture in a pipeline, they were introduced into a polymerization vessel via a pipeline 0.2 m long with an inner diameter (diameter) of 4.5 mm. Next, a triisobutylaluminum solution was added. The reactor was operated under stirring. A discharge pipeline was located at the bottom of the polymerization vessel. Water was added to the discharge pipeline along with tri(2,4-di-tert-butylphenyl) phosphite to stop the polymerization reaction. The product was then heated in a heat exchanger and fed into a defoliation unit. Polymer pellets were obtained using an extruder and an underwater pelletizer.

[0136] The specific process conditions and results are shown in Table B1. [Table 4]

[0137] [Examples B5-B7] The polymerization procedure of Example B1 was used, except that the main catalyst mixture and co-catalyst mixture were measured using a pump and mass flow meter, mixed in a pipeline, and then introduced into the reactor via a pipeline 1 m long with an inner diameter of 4.5 mm.

[0138] The specific process conditions and results are shown in Table B2. [Table 5]

[0139] [Examples B8-B10] The polymerization procedure of Example B1 was used, except that the main catalyst mixture and co-catalyst mixture were measured using a pump and mass flow meter, mixed in a pipeline, and then introduced into the reactor via a pipeline 2 m long with an inner diameter of 4.5 mm.

[0140] The specific process conditions and results are shown in Table B3. [Table 6]

[0141] [Examples B11-B13] The polymerization procedure of Example B1 was used, except that the main catalyst was dimethylsilylbis(5,6,7,8-tetrahydro-2,5,5,8,8-pentamethylbenzindenyl) zirconium dichloride (see U.S. Patent US60 / 586465 for its synthesis method). The co-catalyst was product MMAO-3A purchased from Nouryon Company. The main catalyst mixture and the co-catalyst mixture were measured using a pump and a mass flow meter, mixed in a pipeline, and then introduced into the reactor via a pipeline 0.5 m long with an inner diameter of 4.5 mm.

[0142] The specific process conditions and results are shown in Table B4. [Table 7]

[0143] [Comparative examples B1 to B4] In comparative examples B1 to B4, the main catalyst, co-catalyst, and alkylaluminum were supplied directly to the reactor. [Table 8]

[0144] [Examples C1-C3] The first polymer component (i.e., the propylene copolymer of the present invention) and the second polymer component in the polypropylene composition of the present invention were each produced by continuous polymerization in a 1.8 L polymerization vessel. The polymerization vessel was equipped with a mechanical stirrer. The temperature of the polymerization vessel could be adjusted by controlling the jacket temperature via an oil bath. The temperature inside the reactor was set to 90°C. The polymerization vessel was connected to a propylene pipeline, an ethylene pipeline, an n-hexane pipeline, and a catalyst injection pipeline. The solvent and monomer feeds entering the reactor were measured by a mass flow controller. The flow rate and pressure of the materials were controlled by a variable-speed diaphragm pump. In the production of the first polymer component, the flow rate of propylene was 400 g / h, the flow rate of ethylene was 70 g / h, and the flow rate of n-hexane was 600 g / h. In the production of the second polymer component, the flow rate of propylene was 390 g / h, the flow rate of ethylene was 12 g / h, and the flow rate of n-hexane was 600 g / h.

[0145] Two polymer components were prepared under the same conditions from a primary catalyst, a co-catalyst, and triisobutylaluminum. The primary catalyst was dimethylsilylbis(5,6,7,8-tetrahydro-2,5,5,8,8-pentamethylbenzindenyl)dimethylhafnium. Its synthesis method is described in U.S. Patent US60 / 586465. The primary catalyst was mixed with n-hexane solvent, and the resulting primary catalyst mixture had a concentration of 0.1 μmol / mL. The boron-containing compound was the commercially available compound triphenylcarbeniumtetrakis(pentafluorophenyl)borate, which was mixed with n-hexane solvent. The resulting boron-containing compound mixture had a concentration of 0.15 μmol / mL. The primary catalyst mixture, the boron-containing compound mixture, and the triisobutylaluminum solution (n-hexane solution at a concentration of 1 mmol / mL) were measured using a pump and a mass flow meter. The flow rate of the main catalyst mixture was 60 mL / h, and the flow rate of the co-catalyst mixture was 50 mL / h. After mixing the main catalyst mixture and the boron-containing compound mixture in the pipeline, the mixture was introduced into the reactor via a pipeline 0.2 m long with an inner diameter of 4.5 mm. Subsequently, triisobutylaluminum solution (flow rate: 50 mL / h) was added to the pipeline.

[0146] The reactor was operated at 30 bar with stirring. The polymerization vessel has a discharge pipeline at the bottom. Water was added to the discharge pipeline along with tri(2,4-di-tert-butylphenyl) phosphite to halt the polymerization reaction.

[0147] The first polymer component solution and the second polymer component solution obtained in the polymerization vessel were mixed in a stirring tank, and the blended material was heated in a heat exchanger and then fed into a defoliation device. Polymer pellets were obtained using an extruder and an underwater pelletizer.

[0148] The specific process conditions and results are shown in Table C1. The DSC curves of the polypropylene compositions produced in Examples C1 to C3 are shown in Figures C1 to C3, respectively. These curves had only one melting peak. [Table 9]

[0149] [Examples C4-C6] The first polymer component was produced using the polymerization procedure of Example C1, except that the main catalyst mixture and co-catalyst mixture were measured using a pump and a mass flow meter, mixed in a pipeline, and then introduced into the reactor via a pipeline 2 m long with an inner diameter of 4.5 mm.

[0150] The second polymer component was manufactured using the same polymerization procedure as the first polymer component, except that the main catalyst was dimethylsilylbisindenyl zirconium dichloride and the co-catalyst was MMAO-3A purchased from Nouryon Company. Furthermore, the main and co-catalysts were not pre-mixed in the pipeline, but were directly introduced into the polymerization vessel through their respective pipelines.

[0151] The specific process conditions and results are shown in Table C2. [Table 10]

[0152] [Examples C7-C9] The first polymer component was prepared using the polymerization procedure of Example C1.

[0153] The second polymer component was produced using the same polymerization procedure as the first polymer component, except that the main catalyst was dimethylsilylbisindenyl zirconium dichloride and the co-catalyst was MMAO-3A purchased from Nouryon Company. Furthermore, the main and co-catalysts were not pre-mixed in the pipeline, but were directly added to the polymerization vessel through their respective pipelines. In addition, no comonomers were added, and it was a propylene homopolymerization.

[0154] The specific process conditions and results are shown in Table C3. [Table 11]

[0155] [Comparative example D] [Comparative Examples D1-D3] The polymerization procedure of Example B1 was used, except that the main catalyst was a BCNX catalyst manufactured by Sinopec and the co-catalyst was dicyclopentyl dimethoxysilane. The main catalyst mixture and the co-catalyst mixture were measured using a pump and a mass flow meter, mixed in a pipeline, and then introduced into the reactor via a pipeline 0.5 m long with an inner diameter of 4.5 mm.

[0156] The specific process conditions and results are shown in Table D1. [Table 12]

[0157] [Comparative Examples D4-D6] In the following comparative example, the co-catalyst was Nouryon Company's MAO (a toluene solution with an activated aluminum content of 1.5 mmol / mL). The polymerization procedure of Example B1 was used, except that the main catalyst was dimethylsilylbis(5,6,7,8-tetrahydro-2,5,5,8,8-pentamethylbenzindenyl) zirconium dichloride (see U.S. Patent US60 / 586465 for its synthesis method). The co-catalyst was a toluene solution of methylaluminoxane. The main catalyst mixture and the co-catalyst mixture were measured using a pump and a mass flow meter, mixed in a pipeline, and then introduced into the reactor via a pipeline 0.5 m long with an inner diameter of 4.5 mm.

[0158] The specific process conditions and results are shown in Table D2.

[0159] The data in Table D2 shows that polymerization activity was significantly reduced and the ethylene dispersion was >75%. [Table 13]

[0160] [Comparative examples D7 to D9] The polymerization procedure of Example B1 was used for Comparative Examples D7 and D8, except that the main catalyst mixture and co-catalyst mixture were measured using a pump and a mass flow meter, mixed in a pipeline, and then introduced into the reactor via a pipeline 3 m long with an inner diameter of 4.5 mm. In Comparative Example D9, 500 mL of the main catalyst mixture and 300 mL of the co-catalyst mixture were pre-mixed for 30 minutes in a 1.2 L glass container with a stirrer, and then injected into the reactor by pump.

[0161] The specific process conditions and results are shown in Table D3. [Table 14]

[0162] In comparative examples D7 to D9, it was found that the polymerization reaction activity was extremely low.

[0163] [Comparative Examples D10-D12] The polymerization procedure of Example B1 was used, except that the main catalyst mixture and co-catalyst mixture of Comparative Examples D10 to D12 were measured using a pump and a mass flow meter, mixed in a pipeline, and then introduced into the reactor via a pipeline 5 m long with an inner diameter of 4.5 mm.

[0164] The specific process conditions and results are shown in Table D4. [Table 15]

[0165] In comparative examples D10 to D12, it was found that the polymerization reaction was almost inactive.

[0166] [Comparative Examples D13-D15] The polymerization procedure of Example B1 was used, except that the main catalyst was dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride (purchased from Infinity Scientific (Panjin) Co., Ltd.). The co-catalyst was MAO (toluene solution with an activated aluminum content of 1.5 mmol / mL) from Nouryon Company. The main catalyst mixture and the co-catalyst mixture were measured using a pump and a mass flow meter, mixed in a pipeline, and then introduced into the reactor via a pipeline 0.5 m long with an inner diameter of 4.5 mm.

[0167] The specific process conditions and results are shown in Table D5. [Table 16]

[0168] [Example E: Test of aromatic hydrocarbon compound content] Prior to analysis, the samples were left uncovered at room temperature (maximum 25°C) for 7 days. The tests were conducted according to the German Association of the Automotive Industry standard VDA278, with thermal desorption using Gerstel's TDSA, and an Agilent HP6890 gas chromatograph. The carrier gas was helium, and the separation column was 5% phenylmethylsiloxane. The test results were as follows: [Table 17]

[0169] The embodiments of the present invention have been described above. The above description is illustrative and not exhaustive, and this application is not limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art, without departing from the scope and spirit of each embodiment.

[0170] The endpoints and any values disclosed in this specification are not limited to the exact ranges or values, and it should be understood that they include values close to these ranges or values. For numerical ranges, new numerical ranges can be obtained by combining the endpoint values of each range with each other, the endpoint values of each range with individual point values, or individual point values with each other, and these new numerical ranges should be interpreted as specifically disclosed in this specification.

Brief Description of Drawings

[0171] [Figure 1] Figure A1 shows the dynamic mechanical analysis curves of the polypropylene material before and after incorporation of the propylene copolymer of Example A4 of the present invention. [Figure 2] Figure A2 shows the dynamic mechanical analysis curves of the polypropylene material before and after incorporation of the propylene copolymer of Example A6 of the present invention. [Figure 3] Figure A3 shows the crystallization temperatures (measured by DSC test) of polypropylene compositions incorporated with propylene copolymers of Examples A1 - A4 having different ethylene contents, as well as propylene copolymers of Comparative Examples B2 and B3. [Figure 4] Figures C1 - C3 respectively show the DSC curves of the polypropylene compositions produced in Examples C1 - C3. [Figure 5] Figures C1 - C3 respectively show the DSC curves of the polypropylene compositions produced in Examples C1 - C3. [Figure 6] Figures C1 - C3 respectively show the DSC curves of the polypropylene compositions produced in Examples C1 - C3. [Figure 7] Figure D shows the dynamic mechanical analysis curves of the homopolymer polypropylene material before and after incorporation of the propylene copolymer of Comparative Example B1.

Claims

1. A propylene-based copolymer comprising propylene-derived structural units and comonomer-derived structural units, The propylene copolymer comprises 75 to 93% by weight of the propylene-derived structural units and 7 to 25% by weight of the comonomer-derived structural units. The aforementioned comonomer is ethylene and C ４ ~C ２０ It is at least one of the α-olefins, In the propylene copolymer, the degree of comonomer dispersion D ［ＰＣＰ］／［Ｃ］ The percentage is 60% to 70%, and the comonomer dispersion is D ［ＰＣＰ］／［Ｃ］ A propylene copolymer characterized in that the formula is = [PCP] / [C] × 100%, where [PCP] is the amount of monodisperse comonomer structural units in the propylene copolymer, the monodisperse comonomer structural units are comonomer structural units that exist in the form of single comonomer structural units inserted into propylene segments, [C] is the total amount of comonomer structural units in the propylene copolymer, and the weight content of aromatic hydrocarbon compounds in the propylene copolymer is less than 500 ppm.

2. The mmm stereoregularity of the propylene copolymer is 75% to 99%, preferably 80% to 97%. The stereoregularity index m / r of the propylene copolymer is 3 to 15. The density of the propylene copolymer is 0.84 to 0.92 g / cc, preferably 0.85 to 0.89 g / cc, and The propylene copolymer according to claim 1, wherein the propylene copolymer has at least one of the following characteristics: under a load of 2.16 kg, the melt flow rate at 190°C is 100 g / 10 min or less, preferably 20 g / 10 min or less.

3. The propylene copolymer according to claim 1, wherein the comonomer is at least one of ethylene, 1-butene, and 1-hexene, preferably ethylene.

4. The propylene copolymer according to claim 1, wherein the weight content of aromatic hydrocarbon compounds in the propylene copolymer is less than 300 ppm, more preferably less than 200 ppm or less than 100 ppm, even more preferably less than 50 ppm, and most preferably free of aromatic hydrocarbon compounds.

5. comprising a propylene copolymer according to any one of claims 1 to 4, Preferably, the polymer comprises a propylene copolymer according to any one of claims 1 to 3 and at least one other polymer. Polymer composition.

6. The polymer composition is a polypropylene composition, and further comprises the propylene copolymer and polypropylene described in claim 1, according to claim 5.

7. The aforementioned polypropylene composition, (1) 30 to 99.5% by weight, preferably 50 to 99% by weight, more preferably 60 to 95% by weight of the propylene copolymer according to claim 1, and (2) 0.5 to 70% by weight, preferably 1 to 50% by weight, more preferably 5 to 40% by weight of the polypropylene It contains, The polypropylene comprises 95 to 100% by weight of propylene-derived structural units and 0 to 5% by weight of comonomer-derived structural units. The aforementioned comonomer is ethylene and C ４ ~C ２０ The polymer composition according to claim 6, characterized in that it is at least one of α-olefins.

8. The aforementioned polypropylene composition, The glass transition temperature of the polypropylene composition is -29°C or lower, preferably -30°C or lower. The DSC curve of the aforementioned polypropylene composition has only one melting peak. The melting point of the polypropylene composition is higher than 100°C and less than 140°C, preferably less than 130°C, and more preferably less than 120°C. The initial melting temperature of the polypropylene composition is 80°C or higher, preferably 90°C or higher. The enthalpy of fusion of the polypropylene composition is less than 50 J / g, preferably less than 40 J / g. The melting enthalpy of the polypropylene composition is 0.5 to 50 J / g, preferably 5 to 40 J / g, more preferably 10 to 30 J / g, and most preferably 15 to 25 J / g. The degree of crystallinity of the polypropylene composition is less than 20%, preferably less than 15%, and more preferably 5 to 12%. The density of the polypropylene composition is 0.84 to 0.92 g / cc, preferably 0.86 to 0.89 g / cc. The polymer composition according to claim 7, wherein the polypropylene composition has at least one of the following characteristics: under a load of 2.16 kg, the melt flow rate at 190°C is 100 g / 10 min or less, preferably 20 g / 10 min or less.

9. The polymer composition according to claim 6, obtained by mixing the propylene copolymer according to claim 1 and the polypropylene in a molten or solution form.

10. A method for producing a propylene copolymer according to any one of claims 1 to 4, (A) A step of bringing the main catalyst and co-catalyst into pre-contact to form a homogeneous ionic catalyst solution in a solvent in a pipeline connected to the polymerization reactor, and (B) A process in which the homogeneous ionic catalyst solution obtained in step (A) is sent to a polymerization reactor via a pipeline connected to the polymerization reactor, and olefin polymerization is carried out by contacting it with a propylene monomer, one or more comonomers, and any hydrogen to produce the propylene copolymer. A manufacturing method characterized by including the following.

11. The main catalyst is a metallocene catalyst, preferably at least one of the compounds represented by formula (I), 【Chemistry 1】 In formula (I), M is a metal selected from titanium, hafnium, or zirconium; G is carbon, silicon, germanium, tin, or lead; R and R' are each independently hydrogen, and substituted or unsubstituted C １ ~C ２０ hydrocarbyl selected from; each R'' is independently a hydrogen atom, a halogen atom, C １ ~C ２０ hydrocarbyl group, C １ ~C ２０ alkoxy group or C ６ ~C ２０ aryloxy group selected from, these groups being linear, branched or cyclic and optionally substituted with a halogen atom, C １ ~C １０ alkyl, C １ ~C １０ alkoxy, C ６ ~C １０ aryl or C ６ ~C １０ aryloxy; each R''' is independently a hydrogen atom, C １ ~C ２０ hydrocarbyl group, C １ ~C ２０ alkoxy group or C ６ ~C ２０ aryloxy group selected from; Preferably, R and R' are independently hydrogen and substituted or unsubstituted C. １ ~C ２０ Selected from alkyl groups; each R'' independently consists of a hydrogen atom, a halogen atom, and C. １ ~C １２ alkyl group, C １ ~C １２ Alkoxy group or C ６ ~C １２ Selected from aryloxy groups, these groups are linear, branched, or cyclic, and optionally contain a halogen atom, C １ ~C １０ Alkyl, C １ ~C １０ Alkoxy, C ６ ~C １０ Aryl or C ６ ~C １０ It is further substituted with aryloxy; each R''' independently represents a hydrogen atom, C １ ~C １２ alkyl group, C １ ~C １２ Alkoxy group or C ６ ~C １２ Selected from aryloxy groups; More preferably, R and R' are independently hydrogen and substituted or unsubstituted C. １ ~C １２ Selected from alkyl groups; each R'' independently consists of a hydrogen atom, a halogen atom, and C. １ ~C ６ alkyl group, C １ ~C ６ Alkoxy group or C ６ ~C １２ Selected from aryloxy groups, these groups are linear, branched, or cyclic, and optionally contain a halogen atom, C １ ~C ６ Alkyl, C １ ~C ６ Alkoxy, C ６ ~C １０ Aryl or C ６ ~C １０ It is further substituted with aryloxy; each R''' independently represents a hydrogen atom, C １ ~C ６ alkyl group, C １ ~C ６ Alkoxy group or C ６ ~C １２ Selected from aryloxy groups; More preferably, each of R and R' is independently selected from methyl, ethyl, propyl, butyl, pentyl or hexyl; each R'' is independently a hydrogen atom, a halogen atom, C １ -C ３ alkyl group, C １ -C ３ alkoxy group or C ６ -C ８ aryloxy group, and these groups are linear, branched or cyclic, and are optionally further substituted with a halogen atom, C １ -C ３ alkyl, C １ -C ３ alkoxy, C ６ -C ８ aryl or C ６ -C ８ aryloxy; each R''' is independently a hydrogen atom, C １ -C ３ alkyl group, C １ -C ３ alkoxy group or C ６ -C ８ aryloxy group; Most preferably, R and R' are each independently selected from methyl, isopropyl or tert-butyl; each R'' is each independently selected from a hydrogen atom, a halogen atom, methyl, ethyl or propyl; each R''' is each independently selected from a hydrogen atom, methyl, ethyl or propyl, and / or The method for producing a propylene copolymer according to claim 10, wherein the co-catalyst includes a boron-containing compound type co-catalyst and / or an aluminoxane type co-catalyst.

12. The length L of the pipeline through which the main catalyst and co-catalyst pass from the start of the preliminary contact until it enters the polymerization reactor is given by the following formula: 30×W / d ２ ≦L≦1000×W / d ２ (In the formula, the unit of L is m, W is the total flow rate of the main catalyst, the co-catalyst and the solvent, the unit of W is kg / h, d is the inner diameter of the pipeline, and the unit of d is mm) satisfies, Preferably, L is given by the following formula: 40 × W / d ２ ≤L ≤ 900 × W / d ２ Satisfying the conditions, More preferably, L is the following formula: 50 × W / d ２ ≦ L ≦ 800 × W / d ２ The manufacturing method according to claim 10, which satisfies the above condition.

13. In the preliminary contact between the main catalyst and the co-catalyst, the main catalyst mixture and the co-catalyst mixture are mixed. The aforementioned main catalyst mixture is a mixture of the main catalyst and a solvent. The manufacturing method according to claim 10, wherein the co-catalyst mixture is a mixture of the co-catalyst and a solvent.

14. The boron-containing compound type co-catalyst includes a structure represented by formula (II), (Z) ４ B － (II) In formula (II), Z is an optionally substituted phenyl derivative, and any substituent is C １ ~C ６ It is a haloalkyl or halogen group. Preferably, the boron-containing compound type co-catalyst is selected from the group consisting of triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylbenzylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylphenylammonium tetrakis(pentafluorophenyl)borate, and mixtures thereof, the manufacturing method according to claim 11.

15. The solvent is C ４ ~C ２０ The manufacturing method according to claim 10, wherein the hydrocarbon is at least one of linear, branched, or cyclic aliphatic hydrocarbons, preferably at least one of n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, cyclopentane, and cyclohexane, more preferably at least one of n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, cyclopentane, and cyclohexane, and even more preferably at least one of n-pentane, isopentane, n-hexane, isohexane, and cyclohexane.

16. The manufacturing method according to claim 10, wherein the molar ratio of the co-catalyst to the central metal atom M in the main catalyst is 0.5:1 to 5:1, preferably 1:1 to 2:

1.

17. After the commencement of the preliminary contact, alkylaluminum is added to the olefin polymerization system, where the alkylaluminum is added to the pipeline or to the polymerization reactor, preferably to the pipeline. Preferably, the alkylaluminum has a structure represented by formula (III), AlR ３ (III) In equation (III), R is C １ ~C １２ It is hydrocarbyl, preferably C １ ~C １２ Alkyl, more preferably C １ ~C ８ It is alkyl; preferably, the alkylaluminum is at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, and triisooctylaluminum. Preferably, the alkylaluminum is added in the form of an alkylaluminum solution, and the solvent of the alkylaluminum solution is C ４ ~C ２０ The manufacturing method according to claim 10, wherein the aliphatic hydrocarbon is linear, branched, or cyclic, and preferably the same as the solvent used in the preliminary contact.

18. The olefin polymerization is bulk homogeneous polymerization, supercritical polymerization, solution polymerization, or near-critical dispersion polymerization, and is preferably solution polymerization. More preferably, the solvent for solution polymerization is C ４ ~C ２０ The manufacturing method according to claim 10, wherein the solvent for solution polymerization is the same as the solvent used in the preliminary contact, and is at least one of linear, branched, or cyclic aliphatic hydrocarbons, preferably at least one of n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, cyclopentane, and cyclohexane, more preferably at least one of n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, cyclopentane, and cyclohexane, and even more preferably the solvent for solution polymerization is the same as the solvent used in the preliminary contact.

19. The manufacturing method according to claim 10, wherein the polymerization temperature for the olefin polymerization is 60 to 150°C and the polymerization pressure is 0.1 to 10 MPa.

20. A method for using a propylene copolymer according to any one of claims 1 to 4 for producing a polypropylene composition, The use of a propylene copolymer, wherein the polypropylene composition comprises polypropylene and the propylene copolymer; and the propylene copolymer is used as a polypropylene crystallization accelerator.

21. Use of a propylene copolymer according to any one of claims 1 to 4 for producing a polypropylene composition, The use of a propylene copolymer, wherein the polypropylene composition comprises polypropylene and the propylene copolymer; and the propylene copolymer is used as a modifier for the polypropylene material.

22. The use according to claim 21, wherein the propylene copolymer is used as a modifier for the mechanical properties of the polypropylene material.

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