CN112724343A - Polyolefin block copolymer and preparation method thereof - Google Patents
Polyolefin block copolymer and preparation method thereof Download PDFInfo
- Publication number
- CN112724343A CN112724343A CN202110067106.3A CN202110067106A CN112724343A CN 112724343 A CN112724343 A CN 112724343A CN 202110067106 A CN202110067106 A CN 202110067106A CN 112724343 A CN112724343 A CN 112724343A
- Authority
- CN
- China
- Prior art keywords
- block copolymer
- reaction
- polyolefin
- metal complex
- polyolefin block
- 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.)
- Pending
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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/643—Component covered by group C08F4/64 with a metal or compound covered by group C08F4/44 other than an organo-aluminium compound
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a polyolefin block copolymer and a preparation method thereof, and particularly relates to a method for preparing a polyolefin block copolymer, which comprises the steps of taking a hydrocarbon compound as a solvent under the anhydrous and oxygen-free conditions, and placing an olefin monomer in a metal catalyst system for polymerization reaction to obtain a homopolymer serving as a hard segment structure; intermittently introducing another olefin monomer for copolymerization while keeping the introduction of the olefin monomer, precipitating after terminating the reaction, filtering and drying to obtain the polyolefin block copolymer; the molecular weight can be flexibly regulated and controlled by changing the block number, and on the basis of keeping excellent performances of hard-segment polyolefin such as good mechanical property, thermal property, chemical stability, electrical insulation property and the like, the tensile property and impact resistance of the polyolefin are greatly increased by introducing the polyolefin elastomer as a soft segment.
Description
Technical Field
The invention relates to the technical field of block copolymers, in particular to a polyolefin block copolymer and a preparation method thereof.
Background
Polypropylene is a typical partially crystalline thermoplastic resin, with crystallinity typically ranging from 45% to 50%. With the rapid development of industries such as automobiles, household electrical appliances, logistics, communication and the like, the yield of polypropylene is greatly improved, and the polypropylene becomes the fastest-growing general plastic in the last 10 years. In recent years, China puts forward higher requirements on the performance of polypropylene, such as light weight, low cost, high fluidity and the like, and the material with the characteristics has good processing performance, short production period of finished products and larger market demand. The high crystallinity can improve the rigidity of the material, reduce the thickness of the finished product and lighten the quality of the material. Under the current conditions, if the crystallinity of the impact-resistant co-polypropylene can be further improved, the rigidity, the surface hardness, the heat resistance and the like of the impact-resistant co-polypropylene can be improved, the application field of the polypropylene can be greatly expanded, and the additional value of the product can be improved. The high-rigidity impact-resistant co-polypropylene is mainly used for automotive upholsteries, daily necessities and small household appliance shells, and the annual growth rate of the global consumption reaches 4.2 percent. Therefore, the preparation of high-rigidity and impact-resistant polypropylene has become a research hotspot in the field of high polymer materials at present, which is also an important development direction for the development of new grades of polypropylene.
In order to obtain the copolymerized polypropylene with high crystallinity, improve the low-temperature toughness and impact resistance of the polypropylene and further expand the application range of the polypropylene, researchers in the field originally adopt a physical blending method, namely, mechanically kneading the polypropylene and the toughening component to obtain the toughened polypropylene. However, the polypropylene blend toughening component obtained by the physical blending method can only achieve macroscopic uniform mixing and cannot achieve submicroscopic uniform distribution, so that the impact resistance of the polypropylene cannot be obviously improved by utilizing the physical blending method, and the production cost of the impact-resistant polypropylene is also improved by utilizing the physical mechanical blending process. With the development of the preparation process and theoretical research of the polypropylene catalyst, researchers in the field propose and realize a method for directly finishing a blending process in the polymerization process of polypropylene, so that the toughening component and a polypropylene matrix are uniformly distributed in a submicroscopic manner. The process of directly blending in polymerization process generally adopts two-stage method, firstly, propylene homopolymerization is carried out in a polymerization kettle to obtain homopolymerized polypropylene; and in the second step, the copolymerization of propylene and ethylene (alpha-olefin) is carried out in the homopolymerized polypropylene particles, and finally the propylene copolymer is obtained. As shown in the following figures:
such in situ blends of polypropylene and toughening element (typically ethylene-propylene copolymer) obtained directly in the reactor are known as polypropylene in-kettle alloys (PP), impact co-polymer (IPC) or high impact co-polymer (HIPP), collectively referred to as PP in-kettle alloys. At present, PP kettle alloy products are widely applied to the fields of furniture, packaging materials, small household appliances and the like, and the application of the PP kettle alloy products in automobile parts gradually replaces other high polymer materials to produce a series of products with good performance. However, the product obtained by the alloy in the PP kettle is a blend, the structural form of the product cannot be defined, the molecular weight and the structure are not controllable, and the chemical property is unstable, so that the uniformity of the structure and the standardization of the performance are difficult to achieve in production, and a series of problems that the quality of most products cannot be guaranteed, the comprehensive performance is poor and the like can be caused.
Disclosure of Invention
In order to solve the problems, the invention provides a polyolefin block copolymer and a preparation method thereof, aiming at preparing a polyolefin material mainly based on the polyolefin block copolymer by adopting a polymerization method of sectional feeding and using an improved novel catalyst, and synthesizing the polyolefin block copolymer with high impact resistance, excellent processing fluidity and pressure resistance by adjusting and optimizing polymerization conditions, so that the comprehensive performance of the polyolefin block copolymer is greatly improved, and the polyolefin block copolymer has very high practical value. After the realization of industrialization, the development of the polypropylene industry in China is certainly promoted.
In order to achieve the technical purpose, the invention provides the following technical scheme:
a polyolefin block copolymer consisting of the following structural formula:
hard segment structure:
soft segment structure:
wherein: r1＝0,1,2；R2＝0,1,2,3……X,
The value range of n is 50-70000, and the value range of m is 100-100000.
The invention also provides a preparation method of the polyolefin block copolymer, which comprises the following steps:
under the anhydrous and oxygen-free conditions, hydrocarbon compounds are used as solvents, olefin monomers are placed in a metal catalyst system for polymerization reaction, and homopolymers with hard segment structures are obtained; intermittently introducing another olefin monomer for copolymerization while keeping the introduction of the olefin monomer, precipitating after terminating the reaction, filtering and drying to obtain the polyolefin block copolymer.
Further, the hydrocarbon compound is selected from one of toluene, chlorobenzene and n-hexane.
Further, the olefin monomer includes one of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, and α -olefin.
Further, the metal catalyst system comprises:
(1) a group 4-6 metal complex catalyst;
(2) a scavenging agent;
(3) an activator;
further, the metal complex catalyst has structures of structural formulas (I) and (II), and is selected from one of the structural formulas (I) and (II),
wherein the content of the first and second substances,
M1、M2one selected from titanium, zirconium and hafnium;
R1、R2、R3、R4、R5are respectively selected from hydrogen, halogen, alkyl and naphtheneOne of phenyl, phenyl and phenyl derivatives; r6One selected from the group consisting of alkyl, cycloalkyl, phenyl and phenyl derivatives.
Cp' is a tertiary reagent, and the purity is not less than 99.5 percent.
Still further, the halide includes one of F, Cl, Br, and I.
Further, the scavenging agent is one of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, diethylaluminum chloride, n-butyllithium, triethylaluminum, trimethylaluminum, Triisopropylaluminum (TIBA), triiodobenzoic acid, diethylzinc, diethylmagnesium, dibutylmagnesium and n-butylethylmagnesium.
Further, the activator is selected from triphenylcarbenium tetrakis (pentafluorophenyl) borate ([ Ph)3C][B(C6F5)4]) One of tris (pentafluorophenyl) borane, tri-n-butylammonium tetraphenylborate and triethylammonium tetraphenylborate.
Further, the molar ratio of the scavenging agent to the metal complex catalyst is (100- & ltSUB & gt 3000): 1; the molar ratio of the activator to the metal complex catalyst is (3-1): 1.
Further, the metal catalyst system has certain activity on the polymerization reaction of olefin monomers and the copolymerization reaction of a plurality of olefin monomers.
Further, the polymerization reaction method is selected from one of bulk polymerization, solution polymerization and suspension polymerization.
Further, the reaction conditions are as follows: the temperature is 25-80 ℃, the pressure is 0.1-1MPa, and the reaction time is 1-50 min.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts a one-pot method for preparation, wherein in the first step, a high-density hard-segment copolymer is prepared by adopting a high-activity catalyst system, in the second step, two olefin monomers are simultaneously introduced for copolymerization reaction to prepare a soft-segment copolymer, and the polyolefin multi-block copolymer obtained by repeating the first step and the second step for multiple times of operation is endowed with the characteristics of controllable molecular weight and structure, enhanced tensile resistance, good processing rheological property and the like on the basis of keeping excellent properties of good mechanical property, thermal property, chemical stability, electric insulation property and the like of the hard segment due to the introduction of the olefin elastomer soft segment.
The invention improves the relative molecular mass distribution of polypropylene by improving catalyst and polymerization technology, utilizes common olefin monomer as raw material, obtains block copolymer with alternating soft and hard segments without introducing other polar monomers, improves the isotactic index of polypropylene, thereby improving the crystallization property of polypropylene, uses a one-pot method for preparation, adopts a catalytic system, adjusts the molecular weight through the number of blocks, thereby achieving the purpose of changing the mechanical property, has simple operation, greatly improves the polymerization efficiency, and provides conditions for realizing the wide application of the novel material.
Drawings
FIG. 1 is a high temperature gel permeation chromatogram of a propylene homopolymer and a polyethylene/propylene diblock copolymer according to example 1 of the present invention;
FIG. 2 is a drawing showing a process for preparing a polyethylene/propylene diblock copolymer according to example 1 of the present invention13C NMR spectrum;
FIG. 3 shows the preparation of a polyethylene/propylene diblock copolymer according to example 1 of the present invention1H NMR spectrum;
FIG. 4 is a stress-strain curve of the polyethylene/propylene triblock copolymer of example 2 of this invention;
FIG. 5 is a differential scanning calorimetry curve DSC of a polyethylene/propylene triblock copolymer of example 3 of this invention;
FIG. 6 is a SEM image of a PP/octene pentablock copolymer of example 4 of the present invention.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
Under the anhydrous and oxygen-free conditions, toluene is used as a solvent, a metal catalyst system is filled in a reactor, the temperature in the reactor is controlled to be 25 ℃, the pressure is 0.1MPa, propylene gas is introduced into the reactor for polymerization reaction, and the reaction time is 5min, so that a propylene homopolymer hard segment structure is obtained; and introducing ethylene gas while keeping the introduction of propylene gas, so that ethylene and propylene are subjected to copolymerization reaction in a metal catalyst system, wherein the reaction time is 5min, and precipitating, filtering and drying the mixed solution obtained after the reaction is stopped to obtain the polyethylene/propylene two-block copolymer.
Wherein the metal catalyst system comprises:
A. a hafnium metal complex catalyst; the structure is as follows
B. Triisobutyl aluminum scavenger, the function of triisobutyl aluminum is to treat the reactor;
C. triphenylcarbenium tetrakis (pentafluorophenyl) borate activator;
the molar ratio of the triisobutylaluminum to the hafnium metal complex catalyst is 100: 1;
the molar ratio of triphenylcarbenium tetrakis (pentafluorophenyl) borate to hafnium metal complex catalyst was 2: 1.
The propylene homopolymer and the polyethylene/propylene diblock copolymer prepared in this example were subjected to high temperature gel permeation chromatography, and the results are shown in FIG. 1. As can be seen from FIG. 1, the molecular weight distribution is between 1.0 and 3.0, and the weight average molecular weight can reach 163000 as measured by GPC, with a molecular weight increase of 30000 compared to ethylene homopolymer.
The polyethylene/propylene diblock copolymer prepared in this example was subjected to13C NMR spectral analysis and1the results of H NMR spectrum analysis are shown in FIGS. 2 to 3. As can be seen from the figure, both polyethylene segments and ethylene propylene copolymer segments are present in the copolymer.
Example 2
Under the anhydrous and oxygen-free conditions, chlorobenzene is used as a solvent, a metal catalyst system is added into a reactor, the temperature in the reactor is controlled to be 50 ℃, ethylene gas is introduced into the reactor for polymerization reaction, the gas pressure is 0.5Mpa, and the reaction time is 5min, so that an ethylene homopolymer hard segment structure is obtained; introducing propylene gas under the pressure of 0.5MPa while keeping the introduction of the ethylene gas, so that ethylene and propylene are subjected to copolymerization reaction under a metal catalyst system for 10min to obtain an ethylene/propylene copolymer; stopping introducing the propylene gas, continuing introducing the ethylene gas to carry out polymerization reaction for 10min, precipitating the mixed solution obtained after the reaction is stopped, filtering and drying to obtain the polyethylene/propylene triblock copolymer.
Wherein the metal catalyst system comprises:
A. a hafnium metal complex catalyst; the structure is as follows
B. Diethyl zinc scavenger, the function of diethyl zinc is to treat the reactor;
C. tris (pentafluorophenyl) borane activator;
the molar ratio of the diethyl zinc to the hafnium metal complex catalyst is 200: 1;
the molar ratio of tris (pentafluorophenyl) borane to hafnium metal complex catalyst was 1: 1.
The strain force of the polyethylene/propylene triblock copolymer prepared in this example was analyzed, and as a result, as shown in fig. 4, it can be seen that the elongation at break of the triblock copolymer was 1100%.
Example 3
Under the anhydrous and oxygen-free conditions, using normal hexane as a solvent, adding a metal catalyst system into a reactor, controlling the temperature in the reactor to be 80 ℃, introducing propylene gas into the reactor for polymerization reaction, wherein the pressure is 1Mpa, and the reaction time is 5min, so as to obtain a propylene homopolymer hard segment structure; introducing ethylene gas under the pressure of 1Mpa while keeping the introduction of propylene gas, so that ethylene and propylene are subjected to copolymerization reaction under a metal catalyst system for 5min to obtain an ethylene/propylene copolymer; stopping introducing the propylene gas, continuing introducing the ethylene gas to carry out polymerization reaction for 20min, precipitating the mixed solution obtained after the reaction is stopped, filtering and drying to obtain the polyethylene/propylene triblock copolymer.
Wherein the metal catalyst system comprises:
A. a hafnium metal complex catalyst; the structure is as follows
B. The methylaluminoxane scavenging agent is used for treating the reactor;
C. tri-n-butylammonium tetraphenylborate activator;
the molar ratio of the methylaluminoxane to the hafnium metal complex catalyst is 3000: 1;
the molar ratio of tri-n-butylammonium tetraphenylborate to hafnium metal complex catalyst is 3: 1.
The polyethylene/propylene triblock copolymer prepared in this example was thermally scanned and the results are shown in FIG. 5. It can be seen that DSC has double melting points, narrow crystallization range and low glass transition temperature, which indicates that the excellent thermal stability can be maintained after copolymerization.
Example 4
Under the anhydrous and oxygen-free conditions, using normal hexane as a solvent, adding a metal catalyst system into a reactor, controlling the temperature in the reactor to be 25 ℃, introducing propylene gas into the reactor for polymerization reaction, wherein the pressure is 0.1MPa, and the reaction time is 2min, so as to obtain a propylene homopolymer hard segment structure; adding 2mL of 1-octene while keeping the introduction of propylene gas, so that octene and propylene are subjected to copolymerization reaction under a metal catalyst system for 10min to obtain an octene/propylene copolymer, and continuing to introduce propylene gas for reaction for 5 min; then adding 2mL of 1-octene, and carrying out copolymerization reaction with propylene for 10 min; and (3) continuously introducing propylene gas for reaction for 5min, precipitating, filtering and drying the mixed solution obtained after the reaction is ended to obtain the polypropylene/octene pentablock copolymer.
Wherein the metal catalyst system comprises:
A. a zirconium metal complex catalyst; the structure is as follows
B. Triiodobenzoic acid scavenging agent, the triiodobenzoic acid is used for treating the reactor;
C. a tetraphenylboronic acid activator;
the molar ratio of triiodobenzoic acid to zirconium metal complex catalyst is 200: 1;
the molar ratio of tetraphenylboronic acid to zirconium metal complex catalyst is 2: 1.
The polypropylene/octene pentablock copolymer prepared in this example was subjected to electron microscope scanning, and the results are shown in FIG. 6. It can be seen that the block polymer exhibits a distinct bicontinuous phase, the lighter part being the polypropylene phase and the darker part being the copolymer phase.
Example 5
Under the anhydrous and anaerobic conditions, using normal hexane as a solvent, adding a metal catalyst system into a reactor, controlling the temperature in the reactor to be 25 ℃, introducing butylene gas into the reactor for polymerization reaction, wherein the pressure is 0.1MPa, and the reaction time is 20min, so as to obtain a butylene homopolymer hard segment structure; adding 2mL of 1-octene while keeping the introduction of butene gas, so that octene and butene are subjected to copolymerization reaction under a metal catalyst system for 20min to obtain an octene/butene copolymer; keeping the butylene gas introduced, and reacting for 25 min; and adding 2mL of 1-octene again, reacting for 20min, precipitating the mixed solution obtained after the reaction is ended, filtering, and drying to obtain the polybutene/octene tetrablock copolymer.
Wherein the metal catalyst system comprises:
A. a zirconium metal complex catalyst; the structure is as follows
B. The modified methylaluminoxane scavenging agent has the function of treating the reactor;
C. triethylammonium tetraphenylborate as activator;
the molar ratio of the modified methylaluminoxane to the zirconium metal complex catalyst is 2000: 1;
the molar ratio of triethyl ammonium tetraphenyl borate to zirconium metal complex catalyst is 2: 1.
Example 6
Under the anhydrous and oxygen-free conditions, using normal hexane as a solvent, adding a metal catalyst system into a reactor, controlling the temperature in the reactor to be 25 ℃, introducing propylene gas into the reactor for polymerization reaction, wherein the pressure is 0.1Mpa, and the reaction time is 30min, so as to obtain a propylene homopolymer hard segment structure; while keeping the introduction of propylene gas, adding 5mL of 1-hexene to carry out copolymerization reaction between 1-hexene and propylene in a metal catalyst system for 20min to obtain a 1-hexene/propylene copolymer; continuously introducing propylene gas, and reacting for 6 min; then 5mL of 1-hexene is added for reaction for 20 min; and (3) continuously introducing propylene gas, reacting for 10min, precipitating, filtering and drying the mixed solution obtained after the reaction is ended to obtain the polypropylene/1-hexene pentablock copolymer.
Wherein the metal catalyst system comprises:
A. a titanium metal complex catalyst; the structure is as follows
B. Diethyl magnesium scavenger, the function of diethyl magnesium is to treat the reactor;
C. tris (pentafluorophenyl) borane activator;
the molar ratio of the diethyl magnesium to the titanium metal complex catalyst is 100: 1;
the molar ratio of tris (pentafluorophenyl) borane to titanium metal complex catalyst was 2: 1.
Comparative example 1
The difference from example 1 is that no scavenger is added to the catalyst system.
As a result, it was found that: the reactor is not treated by a scavenging agent, the activity of the catalyst is low, the polymerization activity is reduced, and the obtained polyolefin block copolymer has low crystallinity and poor chemical stability.
Comparative example 2
The difference from example 1 is that no activator is added to the catalyst system.
As a result, it was found that: the catalyst activity is lowered, the polymerization activity is lowered, and the period for producing the polyolefin block copolymer is prolonged.
Comparative example 3
The same as in example 1, except that no metal complex catalyst was added to the catalyst system.
As a result, it was found that: no polymerization activity, and no polymer formation.
Comparative example 4
The same as example 1 except that the reaction temperature was 150 ℃.
As a result, it was found that: due to the excessively high reaction temperature, the crystals formed are small and the crystallinity decreases.
Comparative example 5
The difference from example 1 is that the reaction pressure is 5 MPa.
As a result, it was found that: due to the fact that reaction pressure is too high, system viscosity is increased, copolymerization activity is reduced, and crystallinity is reduced, and therefore the obtained polyolefin block copolymer is poor in comprehensive performance.
Comparative example 6
The difference from example 1 is that the reaction time is 70 min.
As a result, it was found that: because the reaction time is too long and the crystallinity is increased, the strength and the rigidity of the obtained polyolefin block copolymer are improved, and the plasticity and the impact toughness are reduced.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A polyolefin block copolymer, wherein the polyolefin block copolymer consists of the following structural formula:
hard segment structure:
soft segment structure:
wherein: r1＝0,1,2；R2＝0,1,2,3……X,
The value range of n is 50-70000, and the value range of m is 100-100000.
2. A process for preparing the polyolefin block copolymer of claim 1, comprising the steps of:
under the anhydrous and oxygen-free conditions, hydrocarbon compounds are used as solvents, olefin monomers are placed in a metal catalyst system for polymerization reaction, and homopolymers with hard segment structures are obtained; intermittently introducing another olefin monomer for copolymerization while keeping the introduction of the olefin monomer, precipitating after terminating the reaction, filtering and drying to obtain the polyolefin block copolymer.
3. The method according to claim 2, wherein the hydrocarbon compound is one selected from the group consisting of toluene, chlorobenzene, and n-hexane.
4. The method of claim 2, wherein the olefin monomer comprises one of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, and alpha-olefin.
5. The method of claim 2, wherein the metal catalyst system comprises:
(1) a group 4-6 metal complex catalyst;
(2) a scavenging agent;
(3) an activator.
6. The method of claim 5, wherein the metal complex catalyst has the structure of formula (I) or (II), and the metal complex catalyst is selected from one of formula (I) and formula (II),
wherein the content of the first and second substances,
M1、M2one selected from titanium, zirconium and hafnium;
R1、R2、R3、R4、R5are respectively selected from one of hydrogen, halide, alkyl, cycloalkyl, phenyl and phenyl derivatives; r6One selected from the group consisting of alkyl, cycloalkyl, phenyl and phenyl derivatives.
7. The method of claim 5, wherein the scavenger is one of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, diethylaluminum chloride, n-butyllithium, triethylaluminum, trimethylaluminum, triisopropylaluminum, triiodobenzoic acid, diethylzinc, diethylmagnesium, dibutylmagnesium, and n-butylethylmagnesium.
8. The process according to claim 5, wherein the activator is one selected from the group consisting of triphenylcarbenium tetrakis (pentafluorophenyl) borate, tris (pentafluorophenyl) borane, tri-n-butylammonium tetraphenylborate and triethylammonium tetraphenylborate.
9. The method as claimed in claim 5, wherein the molar ratio of scavenging agent to metal complex catalyst is (100- & 3000): 1; the molar ratio of the activator to the metal complex catalyst is (3-1): 1.
10. The method of claim 2, wherein the reaction conditions are: the temperature is 25-80 ℃, the pressure is 0.1-1MPa, and the reaction time is 1-50 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110067106.3A CN112724343A (en) | 2021-01-19 | 2021-01-19 | Polyolefin block copolymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110067106.3A CN112724343A (en) | 2021-01-19 | 2021-01-19 | Polyolefin block copolymer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112724343A true CN112724343A (en) | 2021-04-30 |
Family
ID=75592364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110067106.3A Pending CN112724343A (en) | 2021-01-19 | 2021-01-19 | Polyolefin block copolymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112724343A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275139A (en) * | 1998-08-19 | 2000-11-29 | 蒙特克美国有限公司 | Process for production of heterophasic polymer compositions and compositions thus obtained |
| CN1321140C (en) * | 2002-09-17 | 2007-06-13 | 陶氏环球技术公司 | Improved process for manufacture of polymers |
| CN100424107C (en) * | 2002-01-31 | 2008-10-08 | 三菱化学株式会社 | Non-rigid propylene resin composition |
| CN101331163A (en) * | 2005-09-15 | 2008-12-24 | 陶氏环球技术公司 | Catalytic olefin block copolymers via polymerizable shuttling agent |
| CN101802086A (en) * | 2007-07-13 | 2010-08-11 | 陶氏环球技术公司 | Catalytic olefin block copolymers with controlled block sequence distribution and at least one low crystallinity hard block |
| CN103483482A (en) * | 2013-10-14 | 2014-01-01 | 中国科学院长春应用化学研究所 | Functional isotactic polypropylene and preparation method thereof |
| CN103502290A (en) * | 2011-01-20 | 2014-01-08 | Lg化学株式会社 | Olefin block copolymer |
| CN109748988A (en) * | 2017-11-04 | 2019-05-14 | 天津大学 | A kind of propylene copolymer and preparation method thereof |
| CN111108130A (en) * | 2017-08-04 | 2020-05-05 | 埃克森美孚化学专利公司 | Has the advantages ofcontaining-CH2-SiMe3Hybrid catalysts of partially unbridged hafnocenes |
-
2021
- 2021-01-19 CN CN202110067106.3A patent/CN112724343A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275139A (en) * | 1998-08-19 | 2000-11-29 | 蒙特克美国有限公司 | Process for production of heterophasic polymer compositions and compositions thus obtained |
| CN100424107C (en) * | 2002-01-31 | 2008-10-08 | 三菱化学株式会社 | Non-rigid propylene resin composition |
| CN1321140C (en) * | 2002-09-17 | 2007-06-13 | 陶氏环球技术公司 | Improved process for manufacture of polymers |
| CN101331163A (en) * | 2005-09-15 | 2008-12-24 | 陶氏环球技术公司 | Catalytic olefin block copolymers via polymerizable shuttling agent |
| CN101802086A (en) * | 2007-07-13 | 2010-08-11 | 陶氏环球技术公司 | Catalytic olefin block copolymers with controlled block sequence distribution and at least one low crystallinity hard block |
| CN103502290A (en) * | 2011-01-20 | 2014-01-08 | Lg化学株式会社 | Olefin block copolymer |
| CN103483482A (en) * | 2013-10-14 | 2014-01-01 | 中国科学院长春应用化学研究所 | Functional isotactic polypropylene and preparation method thereof |
| CN111108130A (en) * | 2017-08-04 | 2020-05-05 | 埃克森美孚化学专利公司 | Has the advantages ofcontaining-CH2-SiMe3Hybrid catalysts of partially unbridged hafnocenes |
| CN109748988A (en) * | 2017-11-04 | 2019-05-14 | 天津大学 | A kind of propylene copolymer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| FEI YANG等: ""Effect of Olefin-based Compatibilizers on the Formation of Cocontinuous Structure in Immiscible HDPE/iPP Blends"", 《CHINESE JOURNAL OF POLYMER SCIENCE》 * |
| 任静 等: ""非茂钛配合物催化乙烯/α-烯烃共聚制备聚烯烃弹性体"", 《高分子材料科学与工程》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7071016B2 (en) | Ethylene / alpha-olefin copolymer and its production method | |
| US4245062A (en) | Process for producing propylene-ethylene copolymers | |
| KR101414338B1 (en) | Catalyst component for the polymerization of olefins having a guanidinate ligand | |
| CN1408010A (en) | Crosslinked blends of amorphous and crystalline polymers and their applications | |
| KR101503567B1 (en) | Method of preparing polyolefin | |
| CN104177528B (en) | A kind of ethylene/longer chain α-olefin copolymer and preparation method thereof | |
| EP0703253B1 (en) | Olefinic block copolymer and production process thereof | |
| KR101154508B1 (en) | Hybrid supported metallocene catalysts, method for preparing the same, and method for preparing the polyolefins using the same | |
| CN111788239B (en) | Ethylene/alpha-olefin copolymer and process for producing the same | |
| CN113631604B (en) | Polyolefin-polystyrene multi-block copolymer and preparation method thereof | |
| CN111971313B (en) | Ethylene/alpha-olefin copolymer and process for producing the same | |
| CN108864348B (en) | Ethylene-alpha olefin-non-conjugated diene polymer and preparation method thereof | |
| CN109748988B (en) | Propylene copolymer and preparation method thereof | |
| KR101299650B1 (en) | Polyolefin with multi-modal molecular weight distributions and preparation method thereof | |
| CN112724343A (en) | Polyolefin block copolymer and preparation method thereof | |
| CN112794964B (en) | Propylene-conjugated diene copolymer and preparation method thereof | |
| CN111819213A (en) | Symmetrical polyolefin block copolymer and preparation method thereof | |
| EP3936545A1 (en) | Polyolefin-polystyrene-based multi-block copolymer, and method for producing same | |
| AU651161B2 (en) | Ethylene-propylene copolymer compositions | |
| EP3936546A1 (en) | Polyolefin-polystyrene multiblock copolymer and preparation method therefor | |
| CN114369185B (en) | Homo-polymerized hyperbranched polyethylene and preparation method thereof | |
| CN115232236B (en) | Propylene-based copolymer, preparation method and application thereof, and polypropylene composition | |
| CN106432570B (en) | Propylene-butylene copolymer material and synthesis method for stereotactic controlled polymerization | |
| KR20220015354A (en) | Thermoplastic resin composition | |
| CN116410385A (en) | Polyolefin elastomer, preparation method thereof and metallocene catalyst used in polyolefin elastomer |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210430 |
|
| RJ01 | Rejection of invention patent application after publication |