CN114106453A - Polypropylene composition, polypropylene granules and preparation method thereof - Google Patents
Polypropylene composition, polypropylene granules and preparation method thereof Download PDFInfo
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- CN114106453A CN114106453A CN202010878381.9A CN202010878381A CN114106453A CN 114106453 A CN114106453 A CN 114106453A CN 202010878381 A CN202010878381 A CN 202010878381A CN 114106453 A CN114106453 A CN 114106453A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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Abstract
The invention belongs to the field of polyolefin, and relates to a polypropylene composition, polypropylene granules and a preparation method thereof. The polypropylene composition comprises: (a) and (2) component A: high-crystalline homo-polypropylene with an isotactic pentad fraction of more than 96%; (b) and (B) component: ethylene-propylene elastomeric copolymers; wherein the ratio of the melt mass flow rates of the highly crystalline homopolypropylene to the polypropylene composition at 230 ℃ under a 2.16kg load is from 0.5 to 2.0. The polypropylene granules have high gloss, high rigidity, high toughness and low shrinkage, can be prepared by continuous polymerization, and have economic and convenient preparation method.
Description
Technical Field
The invention belongs to the field of polyolefin, and particularly relates to a polypropylene composition, a preparation method of the polypropylene composition, a polypropylene pellet and a preparation method of the polypropylene pellet.
Background
The polypropylene resin is widely applied in the household appliance and automobile industry, and has the advantages of not only replacing metal and engineering plastics, but also having the characteristics of easy recovery, light weight and relatively low price. These applications require both excellent mechanical properties (stiffness and toughness) and a desirable gloss level for the aesthetic appearance of the article. High-gloss polypropylene is gradually replacing materials such as HIPS (high impact polystyrene), ABS (acrylonitrile butadiene styrene), and the like at present, and is applied to various fields such as electric rice cookers, electric kettles, microwave ovens, dust collectors, washing machine and other household appliance shells, automobile interior parts, children toys, home furnishing storage and the like.
The homo-polypropylene and the random copolymerization polypropylene have high glossiness but poor impact property, and cannot meet the occasions with high requirements on rigidity and toughness. The impact polypropylene has a multiphase structure, so that the rigidity and toughness of the polypropylene are ideal, but the gloss of the polypropylene product is low, and the requirement of high gloss with the gloss of more than 80% (60 DEG angle gloss) cannot be met. The impact polypropylene cannot obviously improve the glossiness by adding a nucleating agent, changing processing conditions and other modes due to the self multiphase structure, and must be adjusted and optimized from the self structure. Although the mechanical properties of the homo-and random-copolymerized polypropylene can be improved by adding POE and other elastomers, the gloss is also affected, and the modification process is complex and high in cost.
CN201310430428.5 discloses a polypropylene composition having both transparency and impact resistance, polypropylene with good transparency, generally with higher gloss. However, the rubber particle size in the transparent impact-resistant polypropylene product is very small, and the rubber has a certain influence on the crystallization of the homopolymerized polypropylene matrix, so that the rigidity of the polypropylene is influenced, and the modulus of the transparent impact-resistant polypropylene product is usually low.
CN201710791552.2 discloses a high-flow high-rigidity high-toughness polyolefin composition and a preparation method thereof, wherein the impact polypropylene has good rigidity and toughness, but is limited by the rubber phase structure, the gloss of the impact polypropylene is low (less than 80%), and the high gloss level cannot be reached.
Therefore, it is highly desirable to find a polypropylene composition which can maintain the good rigidity and toughness balance of the impact polypropylene and has high gloss, which will expand the application range of the polypropylene composition.
Disclosure of Invention
The invention aims to provide a high-gloss high-rigidity high-toughness low-shrinkage impact polypropylene composition, granules and a preparation method thereof.
In a first aspect the present invention provides a polypropylene composition comprising:
(a) and (2) component A: high-crystalline homo-polypropylene having an isotactic pentad fraction of 96% or more, preferably 97% or more;
(b) and (B) component: an ethylene-propylene elastomeric copolymer containing from 25 to 35% by weight of ethylene structural units and from 65 to 75% by weight of propylene structural units, based on the total weight of the ethylene-propylene elastomeric copolymer;
the content of component A is 70-95 wt% and the content of component B is 5-30 wt%, based on the total weight of the polypropylene composition;
wherein the ratio of the melt mass flow rates of the highly crystalline homopolypropylene and the polypropylene composition at 230 ℃ under a load of 2.16kg is from 0.5 to 2.0, preferably from 0.9 to 1.5.
A second aspect of the present invention provides a process for the preparation of the polypropylene composition according to the first aspect of the present invention, comprising the steps of:
(1) under the first olefin polymerization condition, propylene monomer is in contact reaction with a Ziegler Natta catalyst with high stereoselectivity, and unreacted monomer is removed from a mixture obtained after the contact reaction, so that a component A is obtained;
(2) and (2) carrying out contact reaction on ethylene monomer and propylene monomer with the component A obtained in the step (1) under the condition of olefin gas-phase polymerization, and removing unreacted monomers from a mixture obtained after the contact reaction to obtain the polypropylene composition.
A third aspect of the present invention provides a polypropylene pellet comprising:
(i) the polypropylene composition provided by the first aspect of the present invention; and
(ii) an auxiliary agent comprising at least a nucleating agent;
the nucleating agent is present in an amount of 0.05 to 0.3 wt%, based on the total weight of the polypropylene composition.
A fourth aspect of the present invention provides a process for producing the polypropylene pellet according to the third aspect of the present invention, comprising the steps of:
(1) preparing a polypropylene composition according to the process provided in the second aspect of the invention;
(2) mixing and granulating the polypropylene composition obtained in the step (1) and an auxiliary agent at least comprising a nucleating agent to obtain the polypropylene granules.
The polypropylene granules have high gloss, high rigidity, high toughness and low shrinkage, can be prepared by continuous polymerization, and have economic and convenient preparation method.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Exemplary embodiments of the present invention will be described in more detail by referring to the accompanying drawings.
Fig. 1 shows an SEM photograph of the coupon prepared in example 1.
Fig. 2 shows an SEM photograph of the sample wafer prepared in comparative example 2.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In a first aspect the present invention provides a polypropylene composition comprising:
(a) and (2) component A: a highly crystalline homopolypropylene having an isotactic pentad fraction of 96% or more, preferably 97% or more, for example, 97.1%, 97.2%, 97.3%, 97.4%, 97.5%, 97.6%, 97.7%, 97.8%, 97.9%, 98.0%, 98.5%, 99.0% or a range composed of these numerical points;
(b) and (B) component: an ethylene-propylene elastomeric copolymer containing from 25 to 35% by weight of ethylene structural units and from 65 to 75% by weight of propylene structural units, based on the total weight of the ethylene-propylene elastomeric copolymer;
the content of component A is 70-95 wt% and the content of component B is 5-30 wt%, based on the total weight of the polypropylene composition;
wherein the ratio of the melt mass flow rates of the highly crystalline homopolypropylene and the polypropylene composition at 230 ℃ under a load of 2.16kg is from 0.5 to 2.0, preferably from 0.9 to 1.5.
According to a preferred embodiment of the present invention, the high crystalline homopolypropylene has a melt mass flow rate of 5 to 200g/10min, preferably 10 to 100g/10min at 230 ℃ under a load of 2.16 kg.
According to a preferred embodiment of the present invention, the polypropylene composition has a melt mass flow rate at 230 ℃ under a load of 2.16kg of from 5 to 100g/10min, preferably from 6 to 30g/10 min.
From the phase point of view, the polypropylene composition of the present invention comprises a base phase essentially formed by component A and a rubber phase essentially formed by component B dispersed therein. The rubber phase in the polypropylene composition of the present invention is in a conventional form, but has a small particle size, specifically, the rubber phase in the polypropylene composition is spherical or nearly spherical, the average particle size is between 0.1 and 3.0 μm, preferably between 0.1 and 2.0 μm, and unlike the conventional rubber phase, a part of the rubber phase in the polypropylene composition of the present invention is deformed to form an oriented structure after an orientation force is applied. Such as forces exerted on the polypropylene composition during processing such as injection molding. The meaning of the term "oriented state structure" is well known to the person skilled in the art: under the action of some external field (such as tensile stress or shear stress), macromolecular chains, segments or microcrystals can be orderly arranged along the direction of the external field, the orderly parallel arrangement is called orientation, and the formed aggregation state structure is called orientation state structure.
The second aspect of the present invention provides a method for preparing the polypropylene composition, comprising the following steps:
(1) under the first olefin polymerization condition, propylene monomer is in contact reaction with a Ziegler Natta catalyst with high stereoselectivity, and unreacted monomer is removed from a mixture obtained after the contact reaction, so that a component A is obtained;
(2) and (2) carrying out contact reaction on ethylene monomer and propylene monomer with the component A obtained in the step (1) under the condition of olefin gas-phase polymerization, and removing unreacted monomers from a mixture obtained after the contact reaction to obtain the polypropylene composition.
In the present invention, the highly crystalline homopolypropylene having the aforementioned high isotacticity can be obtained and further a mixture of component A and component B can be obtained by using a Ziegler Natta catalyst having a high stereoselectivity, which comprises, according to a preferred embodiment:
(i) a solid catalyst component comprising a product obtained by reacting a magnesium source, a titanium source, and an internal electron donor;
(ii) an organoaluminum compound; and
(iii) optionally an external electron donor;
the internal electron donor is an ester of a monocarboxylic acid and/or an ester of a dicarboxylic acid, preferably at least one of benzoate, malonate, phthalate and succinate, more preferably phthalate, including alkyl phthalate, such as di-isobutyl phthalate and/or di-octyl phthalate, and/or aryl phthalate, such as di-phenyl phthalate and/or di-benzyl butyl phthalate, and/or aryl phthalate, such as di-isobutyl phthalate and/or di-octyl phthalate, with alkyl phthalate being more suitable.
In the present invention, the amount of each component of the solid catalyst component can be determined according to the need, and preferably, the molar ratio of the magnesium source calculated by magnesium element, the titanium source calculated by titanium element and the internal electron donor is 1: 20-150: 0.1 to 0.9, preferably 1: 30-120: 0.15-0.6. The solid catalyst component can be prepared by various methods conventional in the art, for example, the preparation method disclosed in CN 106608934B. The present invention is not particularly limited in this regard.
In the present invention, the amounts of the solid catalyst component, the organoaluminum compound and the external electron donor may also be determined according to the need, and preferably, the ratio of the amount of the solid catalyst component to the amount of the organoaluminum compound in terms of titanium/aluminum molar ratio is 1: 25-100 parts of; the weight ratio of the organic aluminum compound to the external electron donor is 0-150: 1, preferably 2 to 150: 1, more preferably 3 to 10: 1.
in the present invention, the organoaluminum compound is used as a cocatalyst, preferably an alkyl aluminum compound, including but not limited to: triethylaluminium, tri-n-butylaluminium, triisobutylaluminium, tri-n-hexylaluminium, diethylaluminium monochloride, di-n-butylaluminium monochloride, diisobutylaluminium monochloride, di-n-hexylaluminium monochloride, ethylaluminium dichloride, mono-n-butylaluminium dichloride, isobutylaluminium dichloride and n-hexylaluminium dichloride. More preferably, the aluminum alkyl compound is an aluminum trialkyl, such as: at least one of triethylaluminum, tri-n-butylaluminum, and triisobutylaluminum.
According to the invention, the external electron donor is preferably an organosilicon compound having the general formula RnSi(OR')4-nWherein n is more than 0 and less than or equal to 3, R is selected from hydrogen atom, halogen, alkyl, cycloalkyl, aryl and halogenated alkyl, and R' is selected from alkyl, cycloalkyl, aryl and halogenated alkyl. The external electron donor may specifically include, but is not limited to: tetramethoxysilane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl-tert-butyldimethoxysilane, methylisopropyldimethoxysilane, diphenoxydimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane, and (1,1, 1-trifluoro-2-propyl) -methyldimethoxysilane, and the like.
The organosilicon compound as the external electron donor can be added into more than two reactors operated in series together or respectively, can be directly added into the reactors, and can also be added into the related equipment or pipelines for feeding the reactors.
According to the present invention, in the preparation process of the catalyst, the organoaluminum compound and the optional external electron donor may be mixed with the solid catalyst component and then reacted, or the organoaluminum compound and the optional external electron donor may be mixed in advance and then mixed with the solid catalyst component and reacted.
The catalyst of the present invention may be added directly to the reactor or may be added to the reactor after pre-complexing and/or pre-polymerization as is known in the art.
The pre-complexing process may be carried out in an environment with or without polymerized monomer, such as a separately disposed pre-complexing or pre-polymerization reactor. When the pre-complexing reaction is carried out separately, the reactor can be a continuous stirred tank reactor, or can be other forms capable of obtaining sufficient mixing effect, such as a loop reactor, a section of pipeline containing a static mixer, or even a section of pipeline with a material in a turbulent flow state. The temperature of the pre-complexing can be controlled between-10 ℃ and 60 ℃, and the preferable temperature is 0-30 ℃. The pre-complexing time is controlled within 0.1-180min, preferably within 5-30 min.
The catalyst, with or without pre-complexing, may optionally also be subjected to a pre-polymerization treatment. The prepolymerization can be carried out continuously under liquid phase bulk conditions or intermittently in an inert solvent. The prepolymerization reactor can be a continuous stirred tank, a loop reactor, etc. The temperature of the prepolymerization can be controlled between-10 ℃ and 60 ℃, and the preferred temperature is 0-40 ℃. The ratio of prepolymerization is controlled to 0.5-1000 times, preferably 1.0-500 times.
The polymerization according to the invention can be carried out continuously or batchwise. The continuous polymerization may use two or more reactors connected in series. Wherein the first or the first reactors are used for preparing the component A, the reactor for preparing the component A can be a liquid phase reactor or a gas phase reactor, the liquid phase reactor can be a loop reactor or a stirred tank reactor, and the gas phase reactor can be a horizontal stirred bed reactor or a vertical stirred bed reactor or a fluidized bed reactor or a multi-zone circulating reactor, etc. The reactor for preparing the component B of the invention is used for preparing the component B of the invention, the reactor for preparing the component B of the invention is a gas phase reactor, the gas phase reactor can be a horizontal stirred bed reactor, a vertical stirred bed reactor, a fluidized bed reactor and the like, and the gas phase reactor can be matched and combined optionally.
The polymerization according to the invention can be carried out batchwise, with component A according to the invention and component B according to the invention being prepared in succession in the reactor. Wherein the polymerization can be carried out in the liquid phase or in the gas phase for the preparation of component A. The preparation of component B requires polymerization in the gas phase.
According to the present invention, the first olefin polymerization condition in the step (1) may be a liquid phase polymerization condition or a gas phase polymerization condition, and may be a liquid phase polymerization or a gas phase polymerization.
When liquid phase polymerization is adopted, hydrogen is taken as a molecular weight regulator, and the polymerization temperature is 0-150 ℃, preferably 40-100 ℃; the polymerization pressure is higher than the saturation vapor pressure of propylene at the corresponding polymerization temperature.
When gas phase polymerization is adopted, the polymerization temperature is 0-150 ℃, and preferably 40-100 ℃; the polymerization pressure is not less than normal pressure, preferably 0.5 to 2.5 MPa.
According to the present invention, in the gas phase polymerization reaction system of step (2), the molar ratio of ethylene/(ethylene + propylene) is 0.1 to 0.3, preferably 0.15 to 0.25; the gas-phase polymerization of the olefin is carried out at a temperature of 40 to 100 ℃ and preferably 60 to 80 ℃ and at a pressure of 0.6 to 1.4MPa and preferably 1.0 to 1.3 MPa.
The pressure in the present invention is a gauge pressure.
A third aspect of the present invention provides a polypropylene pellet comprising:
(i) the polypropylene composition; and
(ii) an auxiliary agent comprising at least a nucleating agent;
the nucleating agent is present in an amount of 0.05 to 0.3 wt%, based on the total weight of the polypropylene composition.
According to the present invention, the auxiliaries may also include other conventional polymer auxiliaries, for example, at least one of an antioxidant, an antistatic agent and a colorant; the content of the auxiliaries is preferably from 0.1 to 0.6% by weight, based on the total weight of the polypropylene composition.
According to the present invention, preferably, the nucleating agent is at least one selected from the group consisting of carboxylic acids and metal salts thereof nucleating agents, sorbitol nucleating agents, aryl phosphate nucleating agents, dehydroabietic acid and salts thereof nucleating agents, aromatic amide nucleating agents, aromatic amine nucleating agents, rare earth compound nucleating agents, fused ring compound nucleating agents having a quasi-planar structure, and polymer nucleating agents; preferably an organic carboxylate type nucleating agent and/or an aryl phosphate type nucleating agent, such as Millad HPN-20E nucleating agent, Millad HPN-715 nucleating agent, Millad 600EI nucleating agent.
The polypropylene pellets according to the invention preferably have the following characteristics: the 60-degree-angle gloss of the polypropylene composition granules is more than or equal to 80 percent, and preferably the 60-degree-angle gloss is more than or equal to 85 percent; the parallel shrinkage rate is less than or equal to 1.15, and the vertical shrinkage rate is less than or equal to 1.15; the flexural modulus is more than or equal to 1000MPa, the preferred flexural modulus is more than or equal to 1300MPa, and the impact strength of the notch of the simple support beam at room temperature is more than or equal to 5kJ/m2。
In the invention, the glossiness is obtained by measuring injection molding samples according to GB/T8807-1988, and the thickness of the sample is 2 mm; shrinkage was measured on injection molded samples according to GB/T17037.4-2003; the flexural modulus is obtained by measuring an injection molding sample according to GB/T9341-2008; the notch impact strength of the simple supported beam at room temperature is obtained by measuring an injection molding sample at 23 ℃ according to GB/T1043.1-2008.
According to the invention, the rubber phase in the polypropylene granules still remains spherical or nearly spherical, the average particle size is between 0.1 and 3.0 μm, preferably between 0.1 and 2.0 μm, and after the action of the orientation force, part of the rubber phase deforms to form an oriented structure. The meaning of the orientation force and the orientation state structure are as described above and will not be described herein.
The fourth aspect of the present invention provides a method for producing the above-mentioned polypropylene pellets, comprising the steps of:
(1) preparing a polypropylene composition according to the process provided in the second aspect of the invention;
(2) mixing and granulating the polypropylene composition obtained in the step (1) and an auxiliary agent at least comprising a nucleating agent to obtain the polypropylene granules.
The method of mixing and granulating may be various methods conventional in the art, and the present invention is not particularly limited thereto, and for example, granulation may be performed using a twin-screw extruder.
The polypropylene composition and the polypropylene granules can be used in various fields such as household appliances, home furnishing, packaging, toys, automobile modification and the like.
The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to these examples.
Melt Mass Flow Rate (MFR): measured according to GB/T3682.1-2018 at 230 ℃ under a load of 2.16 kg.
Molar ratio of gases in the reactor: measured by gas chromatography.
Xylene solubles content: determined according to GB/T24282-.
Tensile strength: injection molded samples were measured according to GB/T1040.1-2006.
Flexural modulus: injection molded samples were measured according to GB/T9341-.
Impact strength of the simply supported beam notch: injection molded samples were measured at 23 ℃ and-20 ℃ according to GB/T1043.1-2008.
Rockwell hardness: injection molded samples were measured according to GB/T3398.2-2008.
Heat distortion temperature: injection molded samples were measured according to GB/T1634.2-2004.
Gloss: the injection-molded samples were measured according to GB/T8807-1988.
Shrinkage rate: injection molded samples were measured according to GB/T17037.4-2003.
Example 1
This example illustrates the polypropylene composition, polypropylene pellets and process for making the same of the present invention.
(1) Preparation of Polypropylene composition
The polymerization was carried out on a set of polypropylene pilot plants. The polymerization method and the steps are as follows:
preparation of a main catalyst Cat-1: prepared according to the method of example 1 in CN106608934B, 150mL of white oil (commercially available from mingen petrochemical company, inc., guangzhou, with a water content of less than 50ppm by weight), 300mL of methyl silicone oil (commercially available from dow corning with a viscosity of 300 cps/20 ℃ and a water content of less than 50ppm by weight), 30g of magnesium chloride with 0.44 wt% water (commercially available from fushun xin ti o.w.), 50mL of absolute ethanol (commercially available from beijing chemical plant with a water content of less than 100ppm by weight) and 1mL of 2-methoxybenzoyl chloride (commercially available from TOKYO KASEI koyo co.ltd) were added to a 1000mL reaction kettle and heated to 125 ℃ with stirring. After 3 hours of isothermal reaction, the mixture was quenched and formed under 0.3MPa by pressing it through a discharge line pre-fitted with 4 layers of metal mesh having a pore size of 75 μm (0.1 mm per layer thickness) into 2L of hexane (water content less than 5ppm by weight) previously cooled to-30 ℃. The liquid was removed by filtration, and the resulting solid was washed 5 times with 300mL of hexane and dried under vacuum at 30 ℃ for 1.5 hours to obtain a spherical magnesium halide adduct. In a 300mL glass reaction flask, under nitrogen protection, 10mL of hexane, 90mL of titanium tetrachloride were added sequentially, cooled to-20 deg.C, 8.0g of the spherical magnesium halide adduct was added, and stirred at-20 deg.C for 30 minutes. Then, the temperature was slowly raised to 110 ℃ and 1.5mL of diisobutylphthalate was added during the temperature rise. After 30 minutes of isothermal reaction at 110 ℃ the liquid was filtered off. Adding 80mL of titanium tetrachloride, heating to 120 ℃, maintaining the temperature at 120 ℃ for 30 minutes, and filtering out liquid; then, 80mL of titanium tetrachloride was added, the temperature was raised to 120 ℃ and the temperature was maintained at 120 ℃ for 30 minutes, and then the liquid was filtered off. Finally, the solid obtained was washed 5 times with hexane at 60 ℃ (80 mL/time) and dried in vacuo.
Pre-polymerization: after the main catalyst Cat-1 and the internal electron donor diisobutyl phthalate (DIPMS) are subjected to precontacting reaction at 10 ℃ for 20min, the cocatalyst (triethylaluminum) and the external electron donor Diisopropyldimethoxysilane (DIPMS) are continuously added into a prepolymerization reactor for prepolymerization reaction, wherein the flow rate of Triethylaluminum (TEAL) is 6g/hr, the flow rate of diisopropyldimethoxysilane is 1.2g/hr, and the flow rate of the main catalyst is 0.36 g/hr. The prepolymerization is carried out in a propylene liquid phase bulk environment, the temperature is 15 ℃, and the retention time is about 4 min.
The prepolymerized catalyst continuously enters a loop reactor, propylene homopolymerization is completed in the loop reactor, the loop polymerization temperature is 70 ℃, the reaction pressure is 4.0MPa, hydrogen is added into the feeding material of the loop reactor, and the hydrogen concentration detected by online chromatography is 0.15 mol%.
After the loop reactor reacts, the obtained material enters a fluidized bed gas phase reactor to carry out copolymerization reaction of ethylene and propylene. The gas phase reaction temperature was 70 ℃ and the reaction pressure was 1.1MPa, where ethylene/(propylene + ethylene) was 0.21(mol/mol), a certain amount of hydrogen was added to the gas phase reactor feed, and the hydrogen/ethylene in the gas phase reactor recycle gas was 0.13(mol/mol) as detected by line chromatography. The specific process is shown in table 1.
And degassing and deactivating wet nitrogen to obtain the polypropylene composition.
(2) Preparation of Polypropylene pellets
To the polypropylene composition obtained by polymerization, 0.1% by weight of IRGAFOS 168, 0.1% by weight of IRGANOX 1010, 0.05% by weight of calcium stearate, and 0.04% by weight of Millad HPN-20E nucleating agent were added, and pelletized by a twin-screw extruder. Then, an injection molding machine is adopted to prepare an injection molding sample which meets the GB standard, and the physical property of the injection molding sample is measured. The measurement results are shown in Table 2. Fig. 1 shows an SEM photograph of the coupon prepared in example 1. It can be seen that the rubber phase of the polypropylene pellets of example 1 exhibited a distinct oriented structure after injection molding.
Example 2
Example 2 the catalyst system, nucleating agent and polymerisation process conditions used were the same as in example 1. The difference from the embodiment 1 is that: the hydrogen concentration in the loop reactor was 0.23 mol%, and the hydrogen/ethylene ratio in the gas phase reactor was 0.02 (mol/mol). The specific process conditions are shown in Table 1, and the results of the property measurements of the obtained injection molded samples are shown in Table 2.
Example 3
Example 3 the catalyst system, nucleating agent and polymerisation process conditions used were the same as in example 1. The difference from the embodiment 1 is that: the hydrogen concentration in the loop reactor was 0.26 mol%, and in the gas phase reactor, ethylene/(propylene + ethylene) was 0.19(mol/mol) and hydrogen/ethylene was 0.35 (mol/mol). The specific process conditions are shown in Table 1, and the results of the property measurements of the obtained injection molded samples are shown in Table 2.
Example 4
Example 4 the catalyst system, nucleating agent and polymerisation process conditions used were the same as in example 1. The difference from the embodiment 1 is that: the hydrogen concentration in the loop reactor was 0.60 mol%, and in the gas phase reactor, the hydrogen/ethylene ratio was 0.04 (mol/mol). The specific process conditions are shown in Table 1, and the results of the property measurements of the obtained injection molded samples are shown in Table 2.
Comparative example 1
Comparative example 1 the catalyst system, nucleating agent and polymerization process conditions used were the same as in example 1. The difference from the embodiment 1 is that: the hydrogen concentration in the loop reactor was 0.28 mol%, and in the gas phase reactor, ethylene/(propylene + ethylene) was 0.45(mol/mol) and hydrogen/ethylene was 0.01 (mol/mol). The specific process conditions are shown in Table 1, and the results of the property measurements of the obtained injection molded samples are shown in Table 2.
Comparative example 2
Comparative example 2 the catalyst system, nucleating agent and polymerization process conditions used were the same as in example 1. The difference from the embodiment 1 is that: the hydrogen concentration in the loop reactor was 0.70 mol%, and in the gas phase reactor, ethylene/(propylene + ethylene) was 0.45(mol/mol) and hydrogen/ethylene was 0.02 (mol/mol). The specific process conditions are shown in Table 1, and the results of the property measurements of the obtained injection molded samples are shown in Table 2.
Fig. 2 shows an SEM photograph of the sample wafer prepared in comparative example 2. It can be seen that the rubber phase of the polypropylene pellets of comparative example 2 was still substantially spherical after injection molding.
TABLE 1
TABLE 2
As can be seen from the data of Table 2, the polypropylene compositions of the present invention have comparable mechanical properties and higher gloss than those of the polypropylene compositions obtained by the conventional process. The polypropylene composition has both mechanical property and aesthetic property, and has wider application field.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (16)
1. A polypropylene composition, characterized in that it comprises:
(a) and (2) component A: high-crystalline homo-polypropylene having an isotactic pentad fraction of 96% or more, preferably 97% or more;
(b) and (B) component: an ethylene-propylene elastomeric copolymer containing from 25 to 35% by weight of ethylene structural units and from 65 to 75% by weight of propylene structural units, based on the total weight of the ethylene-propylene elastomeric copolymer;
the content of component A is 70-95 wt% and the content of component B is 5-30 wt%, based on the total weight of the polypropylene composition;
wherein the ratio of the melt mass flow rates of the highly crystalline homopolypropylene and the polypropylene composition at 230 ℃ under a load of 2.16kg is from 0.5 to 2.0, preferably from 0.9 to 1.5.
2. The polypropylene composition according to claim 1, wherein the high crystalline homopolypropylene has a melt mass flow rate of 5-200g/10min, preferably 10-100g/10min at 230 ℃ under a 2.16kg load.
3. The polypropylene composition according to claim 1, wherein the polypropylene composition has a melt mass flow rate at 230 ℃ under a 2.16kg load of from 5 to 100g/10min, preferably from 6 to 30g/10 min.
4. The polypropylene composition according to claim 1, wherein the polypropylene composition comprises a base phase and dispersed therein a rubber phase, wherein the rubber phase is spherical or nearly spherical and has an average particle size of between 0.1 and 3.0 μm, preferably between 0.1 and 2.0 μm, and wherein a part of the rubber phase forms an oriented structure upon application of an orienting force.
5. A process for the preparation of a polypropylene composition according to any one of claims 1 to 4 comprising the steps of:
(1) under the first olefin polymerization condition, propylene monomer is in contact reaction with a Ziegler Natta catalyst with high stereoselectivity, and unreacted monomer is removed from a mixture obtained after the contact reaction, so that a component A is obtained;
(2) and (2) carrying out contact reaction on ethylene monomer and propylene monomer with the component A obtained in the step (1) under the condition of olefin gas-phase polymerization, and removing unreacted monomers from a mixture obtained after the contact reaction to obtain the polypropylene composition.
6. The preparation method according to claim 5, wherein the Ziegler Natta catalyst having high stereoselectivity comprises:
(i) a solid catalyst component comprising a product obtained by reacting a magnesium source, a titanium source, and an internal electron donor;
(ii) an organoaluminum compound; and
(iii) optionally an external electron donor;
the internal electron donor is an ester of a monocarboxylic acid and/or an ester of a dicarboxylic acid, preferably at least one of benzoate, malonate, phthalate and succinate, more preferably an alkyl phthalate, and even more preferably diisobutyl phthalate and/or dioctyl phthalate.
7. The production method according to claim 6, wherein the organoaluminum compound is an alkylaluminum compound, preferably at least one of triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diethylaluminum monochloride, di-n-butylaluminum monochloride, diisobutylaluminum monochloride, di-n-hexylaluminum monochloride, ethylaluminum dichloride, mono-n-butylaluminum dichloride, monoisobutylaluminum dichloride and mono-n-hexylaluminum dichloride, further preferably at least one of triethylaluminum, tri-n-butylaluminum and triisobutylaluminum dichloride;
the external electron donor is an organic silicon compound, and the preferred general formula is RnSi(OR')4-nWherein n is more than 0 and less than or equal to 3, R is selected from hydrogen atom, halogen, alkyl, cycloalkyl, aryl and halogenated alkyl, and R' is selected from alkyl, cycloalkyl, aryl and halogenated alkyl; the external electron donor is further preferably tetramethoxysilane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl-tert-butyldimethoxysilane, methylisopropyldimethoxysilane, diphenoxydimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane and (1,1, 1-trifluoro-2-propyl) -methyldimethoxysilane.
8. The preparation method of claim 6, wherein the molar ratio of the magnesium source calculated as magnesium element to the titanium source calculated as titanium element to the internal electron donor is 1: 20-150: 0.1 to 0.9, preferably 1: 30-120: 0.15-0.6; the solid catalyst component and the organic aluminum compound are used in a molar ratio of titanium to aluminum of 1: 25-100 parts of; the weight ratio of the organic aluminum compound to the external electron donor is 0-150: 1, preferably 2 to 150: 1, more preferably 3 to 10: 1.
9. the production method according to any one of claims 5 to 8, wherein the first olefin polymerization conditions of step (1) are liquid phase polymerization conditions or gas phase polymerization conditions;
when liquid phase polymerization is adopted, hydrogen is taken as a molecular weight regulator, and the polymerization temperature is 0-150 ℃, preferably 40-100 ℃; the polymerization pressure is higher than the saturation vapor pressure of propylene at the corresponding polymerization temperature;
when gas phase polymerization is adopted, the polymerization temperature is 0-150 ℃, and preferably 40-100 ℃; the polymerization pressure is not less than normal pressure, preferably 0.5 to 2.5 MPa.
10. The production process according to any one of claims 5 to 8, wherein in the reaction system of step (2), the molar ratio of ethylene/(ethylene + propylene) is from 0.1 to 0.3, preferably from 0.15 to 0.25; the gas-phase polymerization of the olefin is carried out at a temperature of 40 to 100 ℃ and preferably 60 to 80 ℃ and at a pressure of 0.6 to 1.4MPa and preferably 1.0 to 1.3 MPa.
11. A polypropylene pellet, comprising:
(i) the polypropylene composition according to any one of claims 1 to 4; and
(ii) an auxiliary agent comprising at least a nucleating agent;
the nucleating agent is present in an amount of 0.05 to 0.3 wt%, based on the total weight of the polypropylene composition.
12. The polypropylene pellet of claim 11, wherein the coagent further comprises at least one of an antioxidant, an antistatic agent, and a colorant; the content of the auxiliary agent is 0.1-0.6 wt% based on the total weight of the polypropylene composition.
13. The polypropylene pellet as claimed in claim 11, wherein the nucleating agent is at least one selected from the group consisting of carboxylic acids and metal salts thereof, sorbitol nucleating agents, aryl phosphate nucleating agents, dehydroabietic acid and salts thereof, aromatic amide nucleating agents, aromatic amine nucleating agents, rare earth compound nucleating agents, fused ring compound nucleating agents having a quasi-planar structure, and polymer nucleating agents.
14. Polypropylene pellet as claimed in any one of the claims 11-13, wherein the polypropylene composition pellet has a 60 ° gloss of not less than 80%, preferably not less than 85%; the parallel shrinkage rate is less than or equal to 1.15, and the vertical shrinkage rate is less than or equal to 1.15; the flexural modulus is more than or equal to 1000MPa, the preferred flexural modulus is more than or equal to 1300MPa, and the impact strength of the notch of the simple support beam at room temperature is more than or equal to 5kJ/m2。
15. Polypropylene pellet according to any one of claims 11-13, wherein the rubber phase in the polypropylene pellet is spherical or near-spherical with an average particle size between 0.1 and 3.0 μm, preferably between 0.1 and 2.0 μm, and wherein part of the rubber phase forms oriented structures upon application of an orienting force.
16. A process for the preparation of polypropylene pellets as claimed in any one of claims 11 to 15, comprising the steps of:
(1) preparing a polypropylene composition according to the process of any one of claims 5-10;
(2) mixing and granulating the polypropylene composition obtained in the step (1) and an auxiliary agent at least comprising a nucleating agent to obtain the polypropylene granules.
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| CN202010878381.9A CN114106453B (en) | 2020-08-27 | 2020-08-27 | Polypropylene composition, polypropylene granules and preparation method thereof |
| PCT/CN2021/113834 WO2022042447A1 (en) | 2020-08-27 | 2021-08-20 | Polypropylene composition, preparation method therefor, and article made therefrom |
| KR1020237009440A KR20230052957A (en) | 2020-08-27 | 2021-08-20 | Polypropylene composition, method for preparing the same, and articles made therefrom |
| EP21860284.5A EP4206276A1 (en) | 2020-08-27 | 2021-08-20 | Polypropylene composition, preparation method therefor, and article made therefrom |
| JP2023513398A JP2023538693A (en) | 2020-08-27 | 2021-08-20 | Polypropylene compositions, methods for their preparation, and products manufactured using them |
| AU2021332812A AU2021332812A1 (en) | 2020-08-27 | 2021-08-20 | Polypropylene composition, preparation method therefor, and article made therefrom |
| CN202180056674.1A CN116157468A (en) | 2020-08-27 | 2021-08-20 | Polypropylene composition, preparation method thereof and product prepared from polypropylene composition |
| US18/042,481 US20230323099A1 (en) | 2020-08-27 | 2021-08-20 | Polypropylene Composition, Preparation Method therefor, and Article Made therefrom |
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