CN111378062B - Industrial production method of high-melt-strength polypropylene resin - Google Patents
Industrial production method of high-melt-strength polypropylene resin Download PDFInfo
- Publication number
- CN111378062B CN111378062B CN202010382837.2A CN202010382837A CN111378062B CN 111378062 B CN111378062 B CN 111378062B CN 202010382837 A CN202010382837 A CN 202010382837A CN 111378062 B CN111378062 B CN 111378062B
- Authority
- CN
- China
- Prior art keywords
- reactor
- melt strength
- polypropylene
- high melt
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses an industrial production method of high melt strength polypropylene resin. In a gas-phase fluidized bed reactor, polypropylene is produced by using a Ziegler-Natta titanium catalyst, and is subjected to melt extrusion granulation with an additive, so that the obtained polypropylene resin product has high melt strength and good impact strength, tensile strain hardening characteristic and processability. The product is mainly used as a foaming polypropylene raw material and applied to the industries of packaging, automobile parts, buildings, sports goods and the like, and can be used for manufacturing packaging cushions, automobile headrests, cushions, life jackets, surfboards, sound insulation materials and the like.
Description
Technical Field
The invention relates to a foamed polypropylene (EPP) material, in particular to an industrial production method of a high-melt-strength polypropylene resin.
Background
For high melt strength polypropylene, the melt index and melt strength of the product are important physical indicators, which determine the processability and application area of the product. The high melt strength polypropylene resin is a recyclable and reusable environment-friendly material, and a foamed product processed by using the high melt strength polypropylene resin has the characteristics of light weight, high strength, excellent shock resistance, good heat resistance and the like, has lower density than polyethylene and polystyrene foams, has higher strength and heat resistance, can be widely applied to the fields of packaging, automobiles, buildings, sports goods, heat insulation and sound insulation materials and the like, and can replace the traditional foam materials such as polystyrene, polyurethane and the like.
Ordinary polypropylene cannot provide a high foaming ratio, cannot obtain a uniform closed cell structure, and cannot be directly used for foaming because of low melt strength and no branched structure, cannot lock a resin inner bubble structure required in a foaming process, and avoids breakage of a microporous wall. The high melt strength polypropylene currently supplied to domestic and foreign markets is mainly obtained by a post-modification means. The melt strength of polypropylene can be improved by increasing the molecular weight, but the downstream processing is not facilitated, so when the high melt strength polypropylene is produced by the double reactors, the polypropylene molecular weights in the two reactors are respectively controlled, and the polypropylene products with wider molecular weight distribution and different molecular weights are produced.
At present, more manufacturers capable of providing polypropylene products with high melt strength exist in the market. However, most of the products of the brands are high melt strength polypropylenes obtained by adding a high molecular weight polypropylene component, and only high melt strength polypropylene products of northern Europe chemical industry, Japan JPP company, Exxon Mobil company in the United states, and China Petroleum-smoothing petrochemical company have long branched chain structures. The long-chain branched polypropylene (LCB-PP) not only has higher melt strength, but also has the melt tensile strain hardening characteristic, and has excellent foaming performance (especially suitable for green and environment-friendly supercritical CO) 2 Foaming system) can be applied to the high-end (foaming) field. The long-chain branched polypropylene with excellent performance is mainly obtained by a ray irradiation method or a metallocene catalysis polymerization method.
Chinese patent CN 106565870a discloses an olefin polymerization catalyst and its preparation method, an olefin polymerization catalyst system and its application, and a preparation method of polyolefin resin, the patent utilizes a modified olefin polymerization catalyst to complete the preparation of polyolefins such as high melt strength homo-polypropylene in liquid phase, compared with the traditional high melt strength polypropylene, the prepared polypropylene has a branched chain structure, rather than increasing the melt strength of the resin by increasing the molecular weight distribution alone, thus not only having higher melt strength, but also having obvious tensile strain hardening characteristics.
At present, no report on developing and producing high melt strength polypropylene resin with wider molecular weight distribution, branched structure, higher melt strength and remarkable tensile strain hardening characteristic on INEOS innoven gas phase fluidized bed process equipment is seen.
Disclosure of Invention
The invention aims to provide an industrial production method of a high-melt-strength polypropylene resin.
In order to achieve the purpose, the invention adopts the following technical scheme:
an industrial production method of high melt strength polypropylene comprises the following steps:
propylene is used as a main raw material, ethylene is used as a comonomer (the comonomer is not needed to be added when producing high-melt-strength homopolymerized polypropylene, and the ethylene is needed to be added as the comonomer when producing high-melt-strength random copolymerization polypropylene), and hydrogen is used as a molecular weight regulator to prepare the propylene homopolymerized high-melt-strength polypropylene or prepare the ethylene and propylene random copolymerization high-melt-strength polypropylene (such as impact copolymerization polypropylene) through catalytic polymerization.
Preferably, the industrial production method of polypropylene adopts two gas-phase fluidized bed reactors connected in series (for example, two reactors in an INEOS innoven gas-phase fluidized bed series process are used as a first reactor and a second reactor) to synthesize polypropylene.
Preferably, the industrial production method of the polypropylene specifically comprises the following steps:
the first stage is as follows: adding a main catalyst, a cocatalyst, a functional assistant, propylene and hydrogen into the first reactor, or adding the main catalyst, the cocatalyst, the functional assistant, the propylene, the ethylene and the hydrogen into the first reactor; controlling the reaction conditions of the first reactor: the concentration of the propylene is 70-99 mol%, the concentration of the hydrogen is 0.01-10 mol%, the reaction pressure is 1.0-2.5Mpa, the reaction temperature is 40-90 ℃, and the molecular weight of the generated polypropylene can be adjusted by adjusting the adding amount of the hydrogen in the first reactor; after the first reactor stays for 0.5-2 hours, the polypropylene produced in the first reactor enters a second reactor through an airlock system, and the melt index of the polypropylene produced in the first reactor is 0.1-10g/10min (by controlling the hydrogen/propylene ratio).
And a second stage: continuously reacting in a second reactor (including monomer polymerization and further polymerization of polypropylene generated by the first reactor after the polypropylene enters the second reactor) by using a main catalyst, a cocatalyst and a functional auxiliary agent which enter the second reactor through an airlock system, and propylene and hydrogen which are additionally added into the second reactor or propylene, ethylene and hydrogen which are additionally added into the second reactor; controlling the reaction conditions of the second reactor: the concentration of the propylene is 70-99 mol%, the concentration of the hydrogen is 0.1-15 mol%, the reaction pressure is 1.0-2.5Mpa, the reaction temperature is 40-90 ℃, and the molecular weight of the generated polypropylene can be adjusted by adjusting the adding amount of the hydrogen in the second reactor; the polypropylene enters a deactivation system after staying for 0.5 to 2 hours in a second reactor, and the melt index of the polypropylene generated by the second reactor is 0.1 to 10g/10min (by controlling the hydrogen/propylene ratio);
in the two stages, ethylene is not required to be added when the high melt strength homopolymerized polypropylene is produced, and the ethylene serving as a comonomer is added into the two reactors for participating in the reaction when the high melt strength random copolymerization polypropylene is produced, wherein the ethylene concentration is 0.1-20 mol%.
Preferably, the functional auxiliary agent is selected from the general formula R1 m SiX n (OR2) k Wherein R1 is a hydrocarbon group of C2-C20 and R1 contains an α -olefin double bond, a norbornene group, a cycloolefin group or a dicyclopentadiene group at the terminal, X is a halogen, R2 is a linear, branched or isomerized alkyl group of C1-C20, m is an integer of 1-3, n is an integer of 1-3, k is an integer of 0-2, and m + n + k is 4, the amount of the functional assistant used is 1-20 Kg/h.
Preferably, the procatalyst is selected from titanium based catalysts (e.g., Ziegler-Natta type); the dosage of the main catalyst is 0.5-20 Kg/h.
Preferably, the cocatalyst is selected from one or more of an aluminum alkyl (e.g., triethylaluminum), an external electron donor; the dosage of the alkyl aluminum is 1 to 20Kg/h, and the dosage of the external electron donor is 0.5 to 10 Kg/h.
Preferably, the external electron donor is selected from one or more of carboxylic acids, esters, organic phosphorus compounds, and organic silicon compounds, which can be used as an external electron donor of a titanium-based catalyst such as a Ziegler-Natta catalyst.
Preferably, the external electron donor is selected from one or more of diisobutyldimethoxysilane (DIBDMS), diisopropyldimethoxysilane (DIPDMS), Isobutylisopropyldimethoxysilane (IBMDMS), tetraethyl silicate (TEOS).
Preferably, the reaction conditions of the first reactor are controlled as follows: the hydrogen concentration is 0.01mol percent to 0.1mol percent (for example, 0.03mol percent to 0.08mol percent), the reaction pressure is 1.9 MPa to 2.3MPa, and the reaction temperature is 55 ℃ to 70 ℃; and (3) controlling the reaction conditions of the second reactor: hydrogen concentration of 1.0 mol% to 2.5 mol% (e.g., 1.5 mol% to 2.5 mol%), reaction pressure of 1.9 to 2.3Mpa, reaction temperature of 55 to 70 ℃; the reaction temperature and pressure conditions of the second reactor and the first reactor can be the same.
Preferably, the ethylene concentration in the first reactor and the second reactor is respectively controlled to be 1 mol% to 8 mol%.
Preferably, the high melt strength polypropylene is a propylene homopolymer or a random copolymer of propylene and ethylene, wherein the content of propylene structural units in the copolymer is 80 wt% to 99 wt%, and the content of ethylene structural units in the copolymer is 1 wt% to 20 wt%.
An industrial production method of a high melt strength polypropylene resin, comprising the steps of:
1) preparing high melt strength polypropylene (propylene homopolymer or random copolymer of propylene and ethylene as described above) using two gas phase fluidized bed reactors in series (e.g., two reactors in an INEOS innoven gas phase fluidized bed series process as the first reactor and the second reactor) in the above two stages; carrying out catalytic polymerization reaction under certain temperature and pressure conditions in a first reactor, and enabling a reaction system (comprising a catalyst, an auxiliary agent and the like) to enter a second reactor through an airlock system for continuous reaction;
2) discharging the high melt strength polypropylene (polypropylene powder) generated by the second reactor to a deactivation system, conveying the deactivated polypropylene (polypropylene powder) to an extrusion granulation system by a powder conveying system, uniformly mixing the powder with the added resin additive in the extrusion granulation system, and then performing melt extrusion granulation to obtain the high melt strength polypropylene resin particles.
Preferably, the high melt strength polypropylene resin comprises 95 to 99.9% of the above high melt strength polypropylene and 0.1 to 5% of a resin additive by mass fraction.
Preferably, the high melt strength polypropylene resin has a melt strength of 5 to 30 cN.
Preferably, the high melt strength polypropylene resin has a melt index of 0.1 to 10g/10 min.
Preferably, the resin additive is selected from one or more of an antioxidant, an acid scavenger (e.g., calcium stearate), a nucleating agent.
Preferably, the formulation of the resin additive is: 50-70 wt% of antioxidant, 20-30 wt% of acid scavenger and 10-20 wt% of nucleating agent.
The invention has the beneficial effects that:
the invention can realize the production of polypropylene powder with higher melt strength and obvious tensile strain hardening characteristic by respectively optimizing and controlling the reaction conditions of the two reactors, the powder is extruded and granulated with resin additives after being deactivated, the melt index of the obtained high melt strength polypropylene resin can be controlled within a set range (0.1-10g/10min), and the melt index and the melt strength of the final resin product can meet the requirements of downstream products by controlling the hydrogen concentration and the addition amount of functional additives of the two reactors.
Furthermore, the invention adopts a gas-phase fluidized bed reactor, uses titanium catalysts such as Ziegler-Natta and the like and functional additives capable of realizing polypropylene molecular branching, and adopts a series operation flow of two reactors, so that the production process is easy to control, and long-period production can be carried out.
Further, the present invention can not only control the molecular weight of the product by adjusting the amount of hydrogen added, but also increase the molecular weight distribution by controlling the melt index of the polymer in the second reactor to be higher than that in the first reactor.
Drawings
FIG. 1 is a melt strength measurement curve of a polypropylene resin.
FIG. 2 shows the result of the polypropylene resin melt tensile strain hardening characteristics test.
FIG. 3 is a schematic view showing a process for producing a homo-polypropylene resin having high melt strength.
FIG. 4 is a schematic view of a process for producing a high melt strength random copolymerized polypropylene resin.
Detailed Description
The invention is further described in detail below with reference to the drawings and examples, which are intended to illustrate the invention and not to limit the scope of the invention.
High melt strength polypropylene resin and its industrial production process
The invention utilizes the series operation flow of double horizontal reactors in the INEOS innoven gas phase fluidized bed process, adds the raw material monomer, the main catalyst, the cocatalyst, the functional auxiliary agent and other components into the reactors, carries out polymerization reaction under the conditions of certain temperature (55-70 ℃) and pressure (1.9-2.3Mpa), adopts nitrogen with steam to eliminate residual activity (deactivation for short) in the powder, mixes the polypropylene powder with the resin additive and carries out extrusion granulation, thereby preparing the high melt strength polypropylene resin product which has higher melt strength, good impact strength and tensile strain hardening characteristics.
Test items and adopted standards of polypropylene and corresponding resin products are as follows:
1) melt index (MFR), i.e. melt flow rate: measured according to GB/T3682.
2) Tensile yield stress: measured according to GB/T1040.2.
3) Impact strength: GB/T1843.
4) Flexural modulus: measured according to GB/T9341.
5) Melting point: measured according to GB/T19466.3.
6) Load heat distortion temperature: measured according to GB/T1634.2.
7) Melt strength: a Rheoten melt Strength Meter from Geottfert Werkstoff Pruefmaschen, Germany was used. The apparatus comprises a pair of rollers with opposite rotating directions, polymer is melted and plasticized by a single-screw extruder, then extruded by a circular hole die head which turns 90 degrees, clamped between the two rollers and rotationally stretched in an equal acceleration mode, the stretching force can be measured by a measuring force element, and the maximum force value measured from the beginning of stretching to the fracture of a melt is the melt strength.
Each of the above tests was carried out at ambient conditions at room temperature (15-25 ℃ C.), unless otherwise indicated.
(II) preparation example of high melt Strength Polypropylene resin
Example 1
The polymerization was carried out on an INEOS innoven gas phase fluidized bed process unit. The device mainly comprises a raw material refining unit, a catalyst feeding unit, a polymerization reaction unit and the like. The steps of the preparation method are as follows, see fig. 3:
1.1 raw material refining:
the raw material propylene passes through a raw material refining system to remove various reaction impurities such as water, COS and the like.
1.2 feeding of a main catalyst, a cocatalyst and a functional auxiliary agent:
the main catalyst, the cocatalyst and the functional auxiliary agent are all fed through the catalyst feeding unit.
Commercially available commercial catalyst (Ziegler-Natta titanium based catalyst) was injected into the reactor by spraying it in propylene entrained form by a feed pump.
And (3) spraying and injecting a cocatalyst of triethylaluminum, silane (particularly DIBDMS) and a functional additive (particularly 7-octenyltrichlorosilane) into the reactor in a propylene-entrained manner.
1.3 polymerization reaction:
feeding refined propylene, a main catalyst, a cocatalyst, hydrogen and a functional auxiliary agent into a first reactor through a reactor for reaction, allowing the mixture to stay in the first reactor for 1-1.5 hours, allowing the mixture to enter a second reactor through an airlock system for continuous reaction, adding the refined propylene and the hydrogen into the second reactor during the reaction, allowing the mixture to stay in the second reactor for 1-1.5 hours, discharging a powder product generated by the reaction to a deactivation system through a discharge system, deactivating to obtain polypropylene powder, and conveying the polypropylene powder to an extrusion granulation system through a powder conveying system (a closed nitrogen loop).
1.4 preparation of high melt strength homo-polypropylene resin:
in an extrusion granulation system, mixing is carried out according to the proportion that 1 part by weight of composite additives (antioxidant, calcium stearate and nucleating agent) are added into 99 parts by weight of polypropylene powder, the mixture of the polypropylene powder and the composite additives is melted and extruded by a double-screw extruder for granulation, and the obtained granules are the high melt strength homopolymerized polypropylene resin.
When the high melt strength homo-polypropylene resin is produced, the specific production process control parameters of the two reactors are shown in table 1, and the product performance test results of the high melt strength homo-polypropylene resin obtained by co-extruding and granulating the polypropylene powder produced according to the control parameters and the additive are shown in table 2.
TABLE 1 Process control parameter Table for high melt strength homo-polypropylene resin
Note: the melt index (2.16Kg/230 ℃) of the polymer in the first reactor and the second reactor was 1g/10min and 1.75g/10min, respectively
TABLE 2 Performance test Table for homo-polypropylene resin with high melt strength
Example 2
Referring to fig. 4, the present example achieves the production of a high melt strength random copolymerized polypropylene resin by feeding ethylene in two reactors. The addition of ethylene reduces the regularity of the polypropylene molecular chain, thereby meeting the requirements of downstream processing. The specific process control parameters for the two reactors in the production of high melt strength random copolymer polypropylene resin are shown in Table 3.
TABLE 3 Process control parameter Table for high melt Strength random copolymerized Polypropylene resin
Note: the melt index (2.16Kg/230 ℃) of the polymer in the first reactor and the second reactor was 1g/10min and 2g/10min, respectively
Compared with example 1, the physical parameters of the high melt strength PP-R resin produced in this example are different from those of the high melt strength PP-R resin (example 1) due to the addition of ethylene as a comonomer in both reactors, and the results of the product performance test of the high melt strength PP-R resin obtained by co-extrusion and pelletization of the polypropylene powder produced according to the control parameters shown in Table 3 and the additives are shown in Table 4.
TABLE 4 Performance test Table for high melt strength random copolymerized polypropylene resin
The comparison of the detection results shows that: compared with the high melt strength homopolymerized polypropylene resin, the high melt strength random copolymerization polypropylene resin prepared by adding the comonomer ethylene in the polymerization process has the advantages that the melting point, the load thermal deformation temperature, the bending modulus and the tensile yield stress are all reduced, but the impact strength is improved, and downstream users can select proper high melt strength polypropylene resin products according to requirements.
When the hydrogen concentration of the first reactor is 0.03-0.08 mol% and the hydrogen concentration of the second reactor is 1.5-2.5 mol%, the high melt strength homopolymerized polypropylene powder with the melt index close to 2g/10min can be obtained.
When the hydrogen concentration of the first reactor is 0.03-0.08 mol%, the hydrogen concentration of the second reactor is 1.5-2.5 mol% and the ethylene concentration is 1-8 mol%, the high melt strength random copolymerization polypropylene powder with the melt index close to 2g/10min can be obtained.
The additive is used in the extrusion granulation of the polypropylene powder, so that the resin has better oxidation resistance and the physical property of the resin is improved. Referring to FIG. 1, at different draw rates (0.01 s) -1 、0.1s -1 And 1.0s -1 ) Next, it was found that the melt strength of the high melt strength homo-polypropylene resin reached 28.3 cN. Reflecting that the prepared polypropylene resin has higher melt strength. Referring to FIG. 2, at different draw rates (0.01 s) -1 、0.1s -1 And 1.0s -1 ) In the following, the high melt strength homo-polypropylene resins all show significant tensile strain hardening characteristics.
The resin product prepared by the invention not only effectively controls the change of the melt index of the polypropylene powder in the processing of the resin product, but also has higher melt strength and obvious tensile strain hardening characteristic, thereby effectively improving the processing performance.
In a word, the high melt strength polypropylene resin provided by the invention can realize long-period production (easy process control) by adopting an industrial production method; the polypropylene resin has higher melt strength and obvious tensile strain hardening characteristic, and can be widely popularized and applied in foamed polypropylene products (used for manufacturing packaging cushions, automobile headrests, cushions, life jackets, surfboards, sound insulation materials and the like) in the industries of packaging, automobile parts, sports goods, buildings and the like on a large scale.
Claims (8)
1. An industrial production method of polypropylene with high melt strength is characterized in that: the industrial production method of the polypropylene adopts two gas-phase fluidized bed reactors connected in series as a first reactor and a second reactor, and comprises the following steps:
the first stage is as follows: adding a main catalyst, an auxiliary catalyst, a functional auxiliary agent, propylene and hydrogen into a first reactor to obtain a gas phase reaction system, or adding the main catalyst, the auxiliary catalyst, the functional auxiliary agent, the propylene, the ethylene and the hydrogen into the first reactor to obtain the gas phase reaction system; the gas phase reaction system stays in the first reactor for 0.5 to 2 hours and then enters the second reactor; the reaction conditions of the first reactor were controlled as follows: the molar concentration of hydrogen is 0.01-10%, the molar concentration of ethylene is 1-8%, the reaction pressure is 1.0-2.5Mpa, and the reaction temperature is 40-90 ℃; the melt index of the random copolymerization polypropylene generated by the first reactor is 0.1-10g/10 min; the functional auxiliary agent is selected from a general formula R1 m SiX n (OR2) k Wherein R1 is a C2-C20 hydrocarbon group and the end of R1 contains an α -olefinic double bond, a norbornene group, a cycloolefin group or a dicyclopentadiene group, X is a halogen, R2 is a C1-C20 linear, branched or isomerized alkyl group, m is an integer of 1-3, n is an integer of 1-3, k is an integer of 0-2, and m + n + k is 4, the amount of the functional assistant is 1-20 Kg/h;
and a second stage: continuously carrying out gas-phase polymerization reaction in a second reactor by using a main catalyst, a cocatalyst and a functional auxiliary agent which enter the second reactor from the first reactor, and propylene and hydrogen added into the second reactor or propylene, ethylene and hydrogen added into the second reactor; outputting the corresponding high melt strength polypropylene after the second reactor stays for 0.5 to 2 hours; the reaction conditions of the second reactor were controlled as follows: the molar concentration of hydrogen is 0.1 to 15 percent, the molar concentration of ethylene is 1 to 8 percent, the reaction pressure is 1.0 to 2.5Mpa, and the reaction temperature is 40 to 90 ℃; the melt index of the high melt strength polypropylene produced in the second reactor is 0.1-10g/10 min.
2. An industrial production method of high melt strength polypropylene resin is characterized in that: the industrial production method of the polypropylene resin comprises the following steps:
1) preparing high-melt-strength polypropylene by polymerization reaction by using two gas-phase fluidized bed reactors connected in series as a first reactor and a second reactor
The first stage is as follows: adding a main catalyst, a cocatalyst, a functional assistant, propylene and hydrogen into a first reactor to obtain a gas phase reaction system, or adding the main catalyst, the cocatalyst, the functional assistant, propylene, ethylene and hydrogen into the first reactor to obtain the gas phase reaction system; the gas phase reaction system stays in the first reactor for 0.5 to 2 hours and then enters the second reactor; the reaction conditions of the first reactor were controlled as follows: the molar concentration of hydrogen is 0.01-10%, the molar concentration of ethylene is 1-8%, the reaction pressure is 1.0-2.5Mpa, and the reaction temperature is 40-90 ℃; the melt index of the random copolymerization polypropylene generated by the first reactor is 0.1-10g/10 min; the functional auxiliary agent is selected from a general formula R1 m SiX n (OR2) k Wherein, R1 is a C2-C20 hydrocarbon group and the end of R1 contains an α -olefinic double bond, a norbornene group, a cycloolefin group or a dicyclopentadiene group, X is a halogen, R2 is a C1-C20 linear, branched or isomerized alkyl group, m is an integer of 1-3, n is an integer of 1-3, k is an integer of 0-2, and m + n + k is 4, the dosage of the functional assistant is 1-20 Kg/h;
and a second stage: continuously carrying out gas-phase polymerization reaction in a second reactor by using a main catalyst, a cocatalyst and a functional auxiliary agent which enter the second reactor from the first reactor, and propylene and hydrogen added into the second reactor or propylene, ethylene and hydrogen added into the second reactor; outputting the corresponding high melt strength polypropylene after the second reactor stays for 0.5 to 2 hours; the reaction conditions of the second reactor were controlled as follows: the molar concentration of hydrogen is 0.1-15%, the molar concentration of ethylene is 1-8%, the reaction pressure is 1.0-2.5Mpa, and the reaction temperature is 40-90 ℃; the melt index of the high melt strength polypropylene generated by the second reactor is 0.1-10g/10 min;
2) and (3) deactivating the high melt strength polypropylene, mixing the deactivated high melt strength polypropylene with a resin additive, and performing melting, extrusion and granulation to obtain the high melt strength polypropylene resin.
3. The industrial production method according to claim 1 or 2, characterized in that: the main catalyst is selected from titanium catalysts; the dosage of the main catalyst is 0.5-20 Kg/h.
4. The industrial production method according to claim 1 or 2, characterized in that: the cocatalyst is selected from one or more of alkyl aluminum and external electron donor; the dosage of the alkyl aluminum is 1 to 20Kg/h, and the dosage of the external electron donor is 0.5 to 10 Kg/h.
5. The industrial production method according to claim 1 or 2, characterized in that: the reaction conditions of the first reactor were controlled as follows: the mol concentration of the propylene is 70 to 99 percent, the mol concentration of the hydrogen is 0.01 to 0.1 percent, the reaction pressure is 1.9 to 2.3Mpa, and the reaction temperature is 55 to 70 ℃; the reaction conditions of the second reactor were controlled as follows: the mol concentration of the propylene is 70-99 percent, the mol concentration of the hydrogen is 1.0-2.5 percent, the reaction pressure is 1.9-2.3Mpa, and the reaction temperature is 55-70 ℃.
6. The industrial production method according to claim 1 or 2, characterized in that: the high melt strength polypropylene is a random copolymer of propylene and ethylene; according to the mass fraction, the content of the propylene structural unit in the copolymer is 80-99%, and the content of the ethylene structural unit in the copolymer is 1-20%.
7. The industrial production method according to claim 2, characterized in that: the melt strength of the high melt strength polypropylene resin is 5-30 cN.
8. The industrial production method according to claim 2, characterized in that: the high melt strength polypropylene resin comprises, in mass fraction, 95% to 99.9% of high melt strength polypropylene and 0.1% to 5% of a resin additive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010382837.2A CN111378062B (en) | 2020-05-08 | 2020-05-08 | Industrial production method of high-melt-strength polypropylene resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010382837.2A CN111378062B (en) | 2020-05-08 | 2020-05-08 | Industrial production method of high-melt-strength polypropylene resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111378062A CN111378062A (en) | 2020-07-07 |
| CN111378062B true CN111378062B (en) | 2022-08-26 |
Family
ID=71214436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010382837.2A Active CN111378062B (en) | 2020-05-08 | 2020-05-08 | Industrial production method of high-melt-strength polypropylene resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111378062B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111875726B (en) * | 2020-08-12 | 2023-02-24 | 上海赛科石油化工有限责任公司 | Polypropylene production operation control method |
| CN115073642B (en) * | 2021-03-11 | 2023-11-28 | 中国石油天然气股份有限公司 | High melt strength polypropylene resin and preparation method and application thereof |
| CN115073644A (en) * | 2021-03-11 | 2022-09-20 | 中国石油天然气股份有限公司 | Copolymerized high-melt-strength polypropylene resin and preparation method and application thereof |
| CN115322275A (en) * | 2022-03-07 | 2022-11-11 | 陕西延长中煤榆林能源化工有限公司 | Industrial production method of propylene/1-butene copolymerized polypropylene resin |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788265B (en) * | 2012-10-30 | 2016-12-21 | 中国石油化工股份有限公司 | A kind of polyacrylic preparation method with high fondant-strength |
| EP2796472B1 (en) * | 2013-04-22 | 2017-06-28 | Borealis AG | Two-stage process for producing polypropylene compositions |
| EP2853562A1 (en) * | 2013-09-27 | 2015-04-01 | Borealis AG | Two-stage process for producing polypropylene compositions |
| CN105622808B (en) * | 2014-10-31 | 2018-06-15 | 中国石油化工股份有限公司 | A kind of production method of impact polypropylene |
| CN106432569B (en) * | 2015-08-10 | 2019-03-22 | 中国石化扬子石油化工有限公司 | A kind of preparation method of high melt strength, propylene |
| CN106397643A (en) * | 2016-09-08 | 2017-02-15 | 北方华锦化学工业集团有限公司 | Production method for special polypropylene resin granule material for lithium battery diaphragm |
-
2020
- 2020-05-08 CN CN202010382837.2A patent/CN111378062B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111378062A (en) | 2020-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111378062B (en) | Industrial production method of high-melt-strength polypropylene resin | |
| EP2527376B1 (en) | Preparation method for propylene homopolymer having high melt strength | |
| EP1899415B1 (en) | Propylene polymers having broad molecular weight distribution | |
| KR101083931B1 (en) | Extruded polyolefin for the manufacture of cellular material | |
| CN1137019C (en) | Process for preparation of foamed beads of propylene polymers | |
| KR101840956B1 (en) | Foam produced from polypropylene with low gel content | |
| CN102134291B (en) | Method for preparing polypropylene with high melt strength | |
| EP1642926B1 (en) | Non-crosslinked polyethylene foam | |
| US5962595A (en) | Blend of high-molecular-weight polypropylene and high-molecular weight ethylene-propylene copolymer with broad molecular weight distribution | |
| US20120245302A1 (en) | Method for producing modified propylene polymer | |
| EP2220133B1 (en) | Polypropylene copolymer | |
| CN103665584A (en) | Propylene-ethylene high-melt-strength polypropylene foamed board or sheet and preparation method thereof | |
| JP5203587B2 (en) | Propylene polymer and foam molded article | |
| CN112375171B (en) | Preparation method of polypropylene material | |
| JP2019137847A (en) | Propylene-based polymer composition and foamed molded product thereof | |
| EP3467022B1 (en) | Propylene-based resin composition and injection-molded object thereof | |
| CN114341213A (en) | Polypropylene resin composition, method for producing same, method for producing pre-expanded beads, and method for producing foamed molded article | |
| CN106674720B (en) | High-melt-strength impact-resistant polypropylene foamed bead and preparation method thereof | |
| KR100681869B1 (en) | Soft polyolefin resin with excellent foamming characteristics and foam using the same | |
| CN103183859B (en) | Polyethylene compounding composition containing mico-crosslinking component and pipe products prepared from polyethylene compounding composition | |
| CN101857695A (en) | Method for simultaneously improving impact strength and melt flowability of polypropylene copolymer | |
| KR101995951B1 (en) | A continuous method for manufacturing polyolefin copolymer | |
| CN112375304B (en) | Transparent polypropylene material and preparation method thereof | |
| KR20110085443A (en) | High fuse-bondable polypropylene composition for expanded polypropylene | |
| KR100574681B1 (en) | Polyolefin resin composition with high melt strength and foam produced using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 710000 energy and chemical comprehensive utilization Industrial Park, yangqiaopan Town, Jingbian County, Yulin City, Shaanxi Province Patentee after: Shaanxi Yanchang Zhongmei Yulin Energy and Chemical Co.,Ltd. Address before: 718000 energy and chemical comprehensive utilization Industrial Park, yangqiaopan Town, Jingbian County, Yulin City, Shaanxi Province Patentee before: SHAANXI YANCHANG CHINACOAL YULIN ENERGY CHEMICAL CO.,LTD. |
|
| CP03 | Change of name, title or address |