CN115703858A - Propylene copolymer, preparation method and application thereof - Google Patents
Propylene copolymer, preparation method and application thereof Download PDFInfo
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- CN115703858A CN115703858A CN202110945730.9A CN202110945730A CN115703858A CN 115703858 A CN115703858 A CN 115703858A CN 202110945730 A CN202110945730 A CN 202110945730A CN 115703858 A CN115703858 A CN 115703858A
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 229920001577 copolymer Polymers 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 364
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 83
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 70
- -1 polypropylene Polymers 0.000 claims abstract description 40
- 229920001155 polypropylene Polymers 0.000 claims abstract description 37
- 239000004743 Polypropylene Substances 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 239000000853 adhesive Substances 0.000 claims abstract description 6
- 230000001070 adhesive effect Effects 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 111
- 239000000178 monomer Substances 0.000 claims description 88
- 150000001336 alkenes Chemical class 0.000 claims description 79
- 238000006243 chemical reaction Methods 0.000 claims description 77
- 238000000034 method Methods 0.000 claims description 75
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 75
- 230000008569 process Effects 0.000 claims description 44
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 25
- 239000002685 polymerization catalyst Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 17
- 239000005977 Ethylene Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- 230000000379 polymerizing effect Effects 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 230000003139 buffering effect Effects 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
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- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 8
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 8
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- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Chemical group 0.000 claims description 6
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- 206010051246 Photodermatosis Diseases 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical group [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
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- 229910052719 titanium Inorganic materials 0.000 claims description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical group [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052727 yttrium Chemical group 0.000 claims description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
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- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 4
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
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- 230000008901 benefit Effects 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
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- 238000004062 sedimentation Methods 0.000 description 3
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- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
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- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
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Abstract
The invention relates to a propylene copolymer, the molecular main chain of which comprises a polymerization sequence of propylene units and a polymerization sequence of acrylonitrile units, wherein the polymerization sequences of the propylene units and the polymerization sequences of the acrylonitrile units are alternately arranged, and the structural formula of the propylene copolymer is as follows:
wherein m, m ', n and n' are positive integers, m: n is 20 to 100: n' is 20 to 100. The invention also relates to a preparation method of the propylene copolymer, and a compatilizer, an adhesive, a light aging resistant polypropylene resin and an antistatic polypropylene resin which contain the propylene copolymer and are used for outdoor products. The invention providesThe provided propylene copolymer exhibits good compatibility and adhesion when blended with other polar polymers, while improving the antistatic properties of polypropylene, and the copolymer can maintain this excellent property for a long period of time.
Description
Technical Field
The invention belongs to the technical field of polymer preparation, and particularly relates to a propylene copolymer, and a preparation method and application thereof.
Background
The polypropylene is one of the most widely used polymers at present, has excellent mechanical properties and processability, is a well-known environment-friendly material, and can be completely degraded in a natural environment under certain conditions. However, polypropylene has the greatest disadvantage that it is susceptible to photoaging, so that the lifetime and the range of applications of the material are greatly limited.
For many years, many researchers have desired to solve the technical problem of polypropylene photoaging. Some researchers hope to introduce some polar groups into the polypropylene molecule by chemical modification to improve its photo-aging properties. However, since the polypropylene molecule is a nonpolar molecule, it is not easy to graft a large amount of polar group-containing monomers to the polypropylene molecule by chemical modification means such as grafting.
There are also researchers who wish to improve their properties by blending them with polymers or auxiliaries which have good photoaging properties by physical modification. In the blending method in the prior art, after copolymers with different properties are obtained by respectively polymerizing polymers, the two or more copolymers with different properties are blended to obtain a composition of olefin copolymers; the olefin polymer obtained by the method modifies the performance of the polymer by blending, but on one hand, the polymers with different polarities are difficult to be compatible, and the molecules of the polymers have fluidity, so that the performance of the polymers can be seen to be satisfactory even if the polymers which are temporarily compatible are seen, but the molecules of the different polymers migrate with time, and the molecules forming the blend can seriously migrate into two phases when the molecules are serious.
It has also been reported that blending of various polymers by reactor blending, i.e., preparing different polymers in different reactors and then flowing the melts or solutions of the various polymers together, can be achieved with more uniform properties than typical melt blends; however, it is still difficult to obtain a high value-added olefin polymer having excellent overall properties fundamentally from the level of molecular structure with such reactor blends.
Disclosure of Invention
Based on the above, the main object of the present invention is to provide a propylene copolymer and a preparation method thereof, wherein the propylene copolymer has excellent comprehensive properties, and the preparation method of the propylene copolymer controls the polymerization reaction to apply different reaction conditions in different processes, so that the polymerization process is switched under different reaction conditions according to process design, thereby controlling the molecular structure of the polymer to grow according to the designed molecular chain, and obtaining the propylene copolymer with excellent comprehensive properties; meanwhile, the preparation method of the propylene copolymer also controls the feeding method of the catalyst to ensure that the catalyst components introduced into the polymerization reactor are uniform and the temperature and the pressure are consistent with those of the polymerization reactor, minimizes the influence of the feeding procedure of the catalyst on the polymerization reaction, controls the process conditions of the polymerization reaction, prepares the high-performance polyolefin with designable molecular structure, improves the uniformity and the comprehensive performance of the molecular structure of the product, can avoid the blockage of a feeding pipeline, improves the production efficiency, and is more suitable for practical use.
To this end, the invention provides a propylene copolymer comprising, in its molecular main chain, a polymerized sequence of propylene units and a polymerized sequence of acrylonitrile units, the polymerized sequences of the propylene units and the polymerized sequences of the acrylonitrile units being arranged alternately, the structural formula of which is as follows:
wherein m, m ', n and n' are positive integers, m: n is 20 to 100: n' is 20 to 100.
Preferably, the propylene copolymer described above, wherein the polymerization sequence of the acrylonitrile unit includes a polymerization sequence located in the middle of the molecular chain and a polymerization sequence located at the end of the molecular chain; wherein the content of the polymerization sequences positioned in the middle of the molecular chain is greater than the content of the polymerization sequences positioned at the ends of the molecular chain.
Preferably, the propylene copolymer further comprises 1.0 to 5.0% by mole of acrylonitrile units.
Preferably, the propylene copolymer described above, wherein the weight average molecular weight of the propylene copolymer is 50000 to 1000000.
Preferably, the propylene copolymer has a melt index of 10 to 40g/10min, as measured according to ASTM D1238.
For this purpose, the invention also provides a preparation method of the propylene copolymer, the molecular main chain of the propylene copolymer comprises a polymerization sequence of propylene units and a polymerization sequence of acrylonitrile units, and the polymerization sequence of the propylene units and the polymerization sequence of the acrylonitrile units are alternately arranged; the preparation method of the propylene copolymer comprises the following steps:
(1) In the presence of a propylene polymerization catalyst, introducing a first olefin monomer into a polymerization reactor, and polymerizing under first polymerization conditions;
(2) Introducing a second olefin monomer into the reaction mixture of the step (1) in the presence of a propylene polymerization catalyst, and polymerizing under second polymerization conditions;
(3) Introducing a first olefin monomer into the reaction mixture of the step (2) in the presence of a propylene polymerization catalyst to polymerize the first olefin monomer under first polymerization conditions;
(4) The step (2) and the step (3) are executed and repeated for 2 to 5 times;
(5) Adding a chain terminator to terminate the reaction, filtering and washing to obtain the propylene copolymer.
Preferably, the method further comprises the following steps:
(11) Uniformly mixing a propylene polymerization catalyst with a solvent to obtain a catalyst premix;
(12) The catalyst premixed liquid is sequentially metered, conveyed and buffered, and then is introduced into a polymerization reactor to polymerize a first olefin monomer under the first polymerization condition, and then a second olefin monomer is added to polymerize the second olefin monomer under the second polymerization condition; wherein the metering, delivery and buffering of the premix composition are controlled to be uniform, and the buffer tank pressure is controlled to be the same as the pressure within the polymerization reactor.
Preferably, the process of the preceding, wherein said first polymerization conditions and said second polymerization conditions are carried out alternately in a spatial sequence in the same polymerization reactor; two reaction zones with independently controlled reaction conditions are arranged in the polymerization reactor; each reaction zone is provided with a catalyst feed system.
Preferably, the aforementioned process, wherein said first polymerization conditions and said second polymerization conditions are alternately carried out in a spatial sequence in two polymerization reactors connected in series, respectively; the polymerization reactors are all provided with a catalyst feeding system.
Preferably, the method of the preceding, wherein said metering comprises metering the catalyst premix solution in a metering tank; the metering tank is equipped with a stirring cycle and is metered precisely by a diaphragm metering pump.
Preferably, the method is carried out by using a pipeline provided with a pipeline-structured stirrer.
Preferably, the method further comprises the step of buffering the catalyst premix in a buffer tank, and adjusting the temperature of the premix and the pressure in the buffer tank.
Preferably, the method as described above, wherein the propylene polymerization catalyst comprises a main catalyst and a cocatalyst; wherein, the chemical structural formula of the main catalyst is shown as the following formula:
in the above formula, R 1 And R 2 Each independently selected from one of C1-C20 alkyl, C3-C20 cycloalkyl and C6-C20 aryl; r 3 And R 4 The two are the same or different and are respectively and independently selected from one of hydrogen atoms, C1-C20 alkyl, C3-C20 naphthenic bases and C6-C20 aryl; x is selected from Cl, br, methyl or ethyl; m is selected from titanium, zirconium, hafnium, vanadium, rhodium, iron, nickel, cobalt, neodymium, palladium or yttrium; the cocatalyst comprises an organometallic aluminium compound; further preferably, the cocatalyst is selected from at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum or methylaluminoxane; the mass ratio of the cocatalyst to the main catalyst is 200-800.
Preferably, the method, wherein the solvent is at least one selected from n-hexane, n-heptane or toluene.
Preferably, the method wherein the chain terminator is an ethanolic solution of hydrochloric acid.
Preferably, the method is described in the above, wherein the first olefin monomer is selected from propylene or a mixture of propylene and ethylene, and further preferably, the molar content of propylene in the mixture is greater than or equal to 96%; the second olefin monomer is selected from acrylonitrile monomers.
Preferably, the aforementioned process, wherein the reaction temperature and reaction pressure of said first polymerization condition and said second polymerization condition are the same or different; the first polymerization conditions are: the reaction temperature is 40-75 ℃, and the reaction pressure is 0.5-3.0 Mpa; the second polymerization conditions are: the reaction temperature is 60-90 ℃, and the reaction pressure is 2.0-4.0 Mpa.
Preferably, the method of the previous paragraph, wherein both said first polymerization condition and said second polymerization condition are reacted under an inert gas atmosphere.
The invention also provides a compatilizer which comprises the propylene copolymer and is applied to polyacrylonitrile and polypropylene blends to improve the compatibility of the polyacrylonitrile and polypropylene blends.
The invention also provides an adhesive which comprises the propylene copolymer and is applied to the adhesion of a polypropylene material and a polar polypropylene material so as to improve the adhesion.
The invention also provides a light aging resistant polypropylene resin for outdoor products, which comprises the propylene copolymer.
The invention also provides an antistatic polypropylene resin, which comprises the propylene copolymer.
By means of the technical scheme, the propylene copolymer and the preparation method and application thereof provided by the invention at least have the following advantages:
1. according to the preparation method of the propylene copolymer, the polymerization reaction is switched between the first polymerization condition and the second polymerization condition through process design, the polymerization reaction is alternately carried out, and the molecular chain of the polymer grows different structures in different polymerization stages, so that the propylene copolymer with stable molecular structure and controlled product performance is obtained;
2. according to the propylene copolymer provided by the invention, cyano groups are introduced into a main chain structure of a polypropylene molecule in a certain sequence and quantity, so that the propylene copolymer shows good compatibility and cohesiveness when being blended with other polar polymers, the antistatic property of polypropylene is improved, and the copolymer can keep the excellent performance for a long time;
3. the preparation method of the propylene copolymer provided by the invention can be used for effectively catalyzing the copolymerization of propylene or a mixture of the propylene and ethylene and an acrylonitrile monomer by reasonably selecting and applying the full-heterocyclic non-metallocene compound as the catalyst to prepare the propylene copolymer, and the catalyst has high activity and excellent copolymerization performance, and can be used for the structural design of high added-value products such as the propylene copolymer and the like and the polymer manufacturing process to obtain the propylene copolymer with excellent comprehensive performance.
Drawings
FIG. 1 is a schematic process flow diagram of the process for the preparation of propylene copolymers according to the invention.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and experimental methods without specific conditions noted in the following examples are generally performed under conventional conditions.
The molecular main chain of the propylene copolymer provided by the invention comprises a polymerization sequence of a propylene unit and a polymerization sequence of an acrylonitrile unit; the polymerization sequence of the propylene units and the polymerization sequence of the acrylonitrile units are alternately arranged; the structural formula is as follows:
wherein m, m ', n and n' are positive integers, m: n is 20 to 100: n' is 20 to 100.
Structurally, cyano (CN) in the acrylonitrile is taken as a strong electron-withdrawing group, has a carbon-nitrogen triple bond with strong polarity, and has the volume of only 1/8 of that of methyl; the carbon and nitrogen atoms are connected by triple bonds (one sigma and two pi bonds)) which confer a considerable stability to the cyano group, making it present as a whole in the usual chemical reactions. In the propylene polymer, an acrylonitrile unit is grafted into a molecular chain main chain of the polymer in a form of opening a double bond. In the propylene polymer, the acrylonitrile units can also be positioned at the ends of the molecular chain, but generally, the number of the acrylonitrile units connected to the main chain of the molecular chain is greater than that of the acrylonitrile units connected to the ends of the molecular chain, and the connection length and the connection position can be designed and controlled through process parameters.
Preferably, the polymerization sequence of the acrylonitrile unit includes a polymerization sequence located in the middle of a molecular chain and a polymerization sequence located at an end of the molecular chain; wherein the content of the polymerization sequences positioned in the middle of the molecular chain is greater than the content of the polymerization sequences positioned at the ends of the molecular chain; or a polymerization sequence in which the polymerization sequence of the acrylonitrile unit is located in the middle of the molecular chain; the polymerization sequence positioned in the middle of the molecular chain refers to that different polymerization sequences are connected to two sides of the molecular chain; the polymerization sequence located at the end of the molecular chain means that a different polymerization sequence is linked only to one side thereof.
The acrylonitrile unit is connected with the position and the number of the acrylonitrile units 13 C nuclear magnetic resonance method.
The polymerization sequence of the acrylonitrile unit is in a spiral spatial three-dimensional conformation and is mainly determined by a side group with stronger polarity and larger volume, namely Cyano (CN). Carbon and nitrogen atoms in the cyano group are connected by a trivalent bond, and the structure can absorb photons (ultraviolet light) with more energy and can convert the photons into heat energy, so that a main bond is protected and is not easy to degrade. Therefore, the cyano-modified polypropylene copolymer has excellent stability to sunlight and atmospheric effects. After one year of sunlight and atmosphere, most fibers lose 90 to 95 percent of the original strength, and the strength reduction rate of the propylene copolymer is less than or equal to 30 percent.
Preferably, the percentage content of the acrylonitrile unit is 1.0-5.0% in terms of molar ratio.
The amount of acrylonitrile units incorporated into the backbone of the molecule should be a certain amount to achieve the modification effect, but the amount of incorporated acrylonitrile units should not be too high, which is not only cost effective but also avoids the effect of high incorporated acrylonitrile content on the polypropylene's own performance.
Preferably, the weight average molecular weight of the propylene copolymer is 50000 to 1000000.
In the technical scheme of the invention, an acrylonitrile unit is connected into a main chain of a molecular chain of the copolymer, so that the molecular structure and the comprehensive performance of the propylene copolymer are in a controlled state and basically keep consistent with the design performance of technical personnel. If the time and position of the acrylonitrile incorporation are not controlled from the preparation process, but are only randomly incorporated at the chain ends of the molecular chain, in order to ensure that the copolymer can contain a sufficient number of acrylonitrile units, the molecular weight of the copolymer is greatly reduced, or the polymerization sequence of the acrylonitrile units and the polymerization sequence of the propylene units are polymerized into a longer molecular chain respectively, and the two are difficult to form a stable and controlled molecular structure from the microstructure, so that the product performance is greatly influenced.
The molecular weight distribution of the propylene copolymer was evaluated by gel chromatography (GPC).
Preferably, the melt index is 10 to 40g/10min, as measured according to ASTM D1238.
The preparation method of the propylene copolymer provided by the invention comprises the steps that the molecular main chain of the propylene copolymer comprises a polymerization sequence of a propylene unit and a polymerization sequence of an acrylonitrile unit; the polymerized sequence of propylene units alternating with the polymerized sequence of acrylonitrile units; the preparation method of the propylene copolymer comprises the following steps:
1) In the presence of a propylene polymerization catalyst, introducing a first olefin monomer into a polymerization reactor, and polymerizing under first polymerization conditions;
2) Introducing a second olefin monomer into the reaction mixture in the presence of a propylene polymerization catalyst to polymerize the second olefin monomer under second polymerization conditions;
3) Introducing a first olefin monomer into the reaction mixture in the presence of a propylene polymerization catalyst to polymerize the same under first polymerization conditions;
4) Executing the step 2) and the step 3) for 2-5 times;
5) Adding a chain terminator to terminate the reaction, filtering and washing to obtain the propylene copolymer.
Preferably, the preparation method further comprises the following steps:
11 ) uniformly mixing a propylene polymerization catalyst and a solvent to obtain a catalyst premix; 12 Metering, conveying and buffering the catalyst premixed liquid in sequence, and then introducing the catalyst premixed liquid into a polymerization reactor to respectively polymerize a first olefin monomer under the first polymerization condition and polymerize a second olefin monomer under the second polymerization condition; wherein the metering, the delivering and the buffering of the premix composition are controlled to be uniform, and the pressure of the buffering is controlled to be the same as the pressure in the polymerization reactor.
For convenience of description, in the polymerization process of the present invention, polymerization carried out under first polymerization conditions is defined as first polymerization; the polymerization carried out under the second polymerization conditions is defined as the second polymerization. The first polymerization and the second polymerization are reacted according to a process design sequence.
The first polymerization comprises polymerizing a catalyst with a first olefin monomer; alternatively, the first polymerization comprises polymerizing a catalyst with a first olefin monomer, and the reaction mixture. The second polymerization comprises polymerizing a catalyst with a second olefin monomer, the reaction mixture. The first aggregation and the second aggregation alternately occur in a time series or a spatial series. According to actual needs, certain auxiliary agents can be added in the first polymerization and the second polymerization to help the reaction conditions of the polymerization process to control or adjust the performance of the product. A first auxiliary agent is introduced into the polymerization reactor together with the first olefin monomer in the first polymerization process; and a second auxiliary agent is introduced into the polymerization reactor together with the second olefin monomer in the second polymerization process.
In the prior art, the polymerization modes of the polymer mainly comprise suspension polymerization, emulsion polymerization, bulk polymerization and solution polymerization. At present, the processes of suspension polymerization and emulsion polymerization are developed quite completely, large-scale production is realized, the cost approaches the limit, the method has low universality, and the further development possibility is low technically, so that the method can only be used as a production process of a characteristic polymer in the future; however, although there are technical problems to be solved, the two methods have strong versatility, so that with the development of scientific technology, the polymer manufacturing process gradually moves to bulk polymerization and solution polymerization.
The polymerization process of the present invention may be selected depending on the form of the objective product, and bulk polymerization or solution polymerization is preferably used.
When the application of the product requires solution form, for example as a binder, then both the first and second polymers are solution polymers. In solution polymerization, due to the use of a solvent, the viscosity of a reaction system is reduced, and the solution polymerization is very beneficial to the mixing and heat transfer of materials, so that although the recovery and treatment processes of the solvent are increased due to the use of the solvent, and the solvent has the defects of environmental pollution and the like, the solution polymerization has strong universality, large-scale and continuous production is easy to realize, and the solution polymerization still has good development prospect from the development viewpoint. The technical scheme of the invention preferably prepares the propylene copolymer by the full-heterocyclic non-metallocene compound, which is suitable for a solution polymerization method, can effectively catalyze propylene homopolymerization, propylene and ethylene copolymerization and propylene and acrylonitrile monomer copolymerization, the catalyst has high catalytic activity and excellent copolymerization performance, and the polyolefin product with high added value can be obtained by stepwise polymerization through the technical scheme of the invention.
When the application of the product requires the polypropylene powder form, for example, when used as a resin, then both the first and second polymerization are bulk polymerization. In the bulk polymerization, in order to easily control the severity of the reaction, the catalyst suspension may be pre-polymerized with propylene monomer in advance to control the severity of the reaction in the bulk polymerization and maintain the reaction conditions stable. The technical scheme of the invention preferably prepares the propylene copolymer by the full-heterocyclic non-metallocene compound, which is suitable for a solution polymerization method, can effectively catalyze propylene homopolymerization, propylene and ethylene copolymerization and propylene and acrylonitrile monomer copolymerization, the catalyst has high catalytic activity and excellent copolymerization performance, and the polyolefin product with high added value can be obtained by stepwise polymerization through the technical scheme of the invention.
The first polymerization and the second polymerization may be alternately reacted in time series in the same polymerization reactor; the polymerization reactor is provided with a catalyst feed system. When the first polymerization and the second polymerization occur in the same polymerization reactor, the first polymerization and the second polymerization may be alternately performed in time series, that is, according to "first polymerization reaction-reaction condition switching-second polymerization reaction-reaction condition switching-first polymerization reaction … …"; the reaction route has a transition period when the reaction conditions are switched, so that the control of the reaction conditions is influenced, but the reaction route has the advantages of simple equipment and small occupied space.
The first polymerization and the second polymerization can also be alternately reacted in a spatial sequence in the same polymerization reactor; two reaction zones with independently controlled reaction conditions are arranged in the polymerization reactor; each reaction zone is provided with a catalyst feed system. When at least two reaction zones with independently controlled reaction conditions are arranged in a polymerization reactor, the first polymerization and the second polymerization can be alternately carried out in the polymerization reactor according to a spatial sequence, namely two zones with independently controlled reaction conditions are arranged in the same reactor, the first polymerization is carried out in one zone, and the second polymerization is carried out in the other zone; according to the designed reaction route, the reaction materials are subjected to a first polymerization reaction and a second polymerization reaction alternately in different areas. In the technical scheme of the invention, the detailed structure of the interior of the polymerization reactor is not particularly limited as long as the material can be automatically transferred between the two reaction zones according to the set process time.
The first polymerization and the second polymerization can also be reacted in a spatial sequence in two polymerization reactors connected in series, respectively; the polymerization reactors are all provided with a catalyst feeding system. When the first polymerization and the second polymerization respectively occur in two polymerization reactors connected in series with each other, the materials between the two polymerization reactors can be transferred to each other, the first polymerization and the second polymerization being alternately carried out, that is: the method comprises the steps of first polymerization reaction, material transfer, second polymerization reaction, material transfer and first polymerization reaction … …, and the steps are sequentially subjected to circular reaction.
As shown in the attached figure 1, the technical scheme of the invention adopts the process flow shown in the figure, firstly catalyst is proportioned, the catalyst is proportioned and manufactured according to the designed formula, then the catalyst is fed into a polymerization reactor after being metered and buffered, stirring devices are arranged on the proportioning, metering, buffering and conveying pipelines among all parts so as to keep the components of the catalyst uniform and consistent all the time, prevent the components from being influenced by the sedimentation of the catalyst and avoid the production faults such as the blockage of a conveying pipeline and the like caused by the sedimentation of the catalyst; the catalyst feeding device is respectively connected with a first polymerization reactor and a second polymerization reactor, and can provide catalysts with uniform components and accurate metering for the polymerization reactors so as to accurately control the adding amount and speed of the catalysts. The polymerization is divided into first polymerization and second polymerization, and a first auxiliary agent, a first olefin monomer and a catalyst are introduced into a polymerization reactor according to a designed formula to carry out polymerization under a first polymerization condition; the first olefin monomer may be dissolved or dispersed in a solvent prior to being fed to the polymerization reactor; when the first olefin monomer is a gaseous monomer, then the first olefin monomer is passed directly into the polymerization reactor to dissolve it in the reaction mixture. Prior to mixing, it is generally necessary to purge the solvent and first olefin monomer to remove potential catalyst poisons. And switching the reaction mixture to the second polymerization condition, and adding a propylene polymerization catalyst, a second olefin monomer and a second auxiliary agent for polymerization. The second olefin monomer may be dissolved or dispersed in a solvent prior to being fed into the polymerization reactor for the second polymerization; when the second olefin monomer is a gaseous monomer, then the second olefin monomer is passed directly into the polymerization reactor to dissolve it in the reaction mixture. Prior to mixing, it is generally necessary to purge the solvent and second olefin monomer to remove potential catalyst poisons. And then the reaction mixture is switched to the first polymerization condition, and a propylene polymerization catalyst, a first olefin monomer and a first auxiliary agent are added for polymerization. And designing the process parameters and cycle times of the reverse polymerization according to the molecular weight of the target polymer and the like.
The polymerization reactor is provided with a control center; the control center can receive process control parameters input by engineering technicians and can monitor the polymerization reaction process in real time; in the process of polymerization reaction, the control center can compare the actual condition of the polymerization reaction with the preset cycle number to judge whether the polymerization reaction reaches the set condition, if the polymerization reaction reaches the set condition, the polymerization reaction is finished, and at the moment, a chain terminator is added to terminate the reaction; if the polymerization reaction has not reached the set conditions, the "polymerization under the second polymerization conditions-polymerization under the first polymerization conditions" is cyclically performed.
The polymerization conditions may be determined according to the design of the process route, and for example, the conditions of the first polymerization including at least the kinds and amounts of the first olefin monomer and the first auxiliary, the reaction temperature, the reaction pressure and the reaction time of the first polymerization; the conditions of the second polymerization at least comprise the types and the amounts of the first olefin monomer and the first auxiliary agent, the reaction temperature, the reaction pressure and the reaction time of the first polymerization; and the number of times of alternating reactions of the first polymerization and the second polymerization. The set conditions can be designed according to the experience of technicians, and can also be designed by simulating the polymerization reaction process through a computer; the final determination is preferably carried out by computer simulation of the polymerization process for design in conjunction with the experience of the skilled person.
The polymerization reactors of the first polymerization and the second polymerization are each provided with a stirring system, which may comprise one or more stirrers. Generally the agitator should ensure that the reactants are able to operate with thorough mixing.
According to the invention, the first polymerization reaction and the second polymerization reaction are carried out under different reaction conditions and reaction systems alternately through the process design, so that the molecular structure of the produced polymer is reasonably controlled, and the propylene copolymer product with designable performance and high added value is obtained.
In each step of controlling the accurate metering of the catalyst, the metering comprises the steps of stirring and circulating the catalyst premix liquid in a metering tank and accurately metering by a diaphragm metering pump; the diaphragm metering pump replaces a piston with a specially designed and processed flexible diaphragm, and reciprocating motion is realized under the action of a driving mechanism to complete the suction-discharge process. Due to the isolation of the diaphragm, it is structurally possible to achieve isolation between the fluid being metered and the driving lubrication mechanism.
A pipeline structure stirrer is arranged on the pipeline for conveying; the stirrer with the pipeline structure can force liquid and gas media to convect and mix uniformly, and is composed of two straight blades, so that the generated radial liquid flow velocity is low. The blades of the pitched blade agitator are turned at 45 ° or 60 ° in opposite directions, thus creating axial fluid flow.
The buffering comprises stirring and circulating the catalyst premixed liquid in a buffer tank, and adjusting the temperature of the premixed liquid and the pressure in the buffer tank.
The propylene polymerization catalyst is prepared in an intermittent preparation mode, when catalysts in each batch are switched, the reaction temperature and the internal pressure in a polymerization reactor dynamically change due to the switching process, generally show a trend of descending first and then ascending, so that the polymerization reaction is greatly fluctuated, the operation difficulty is brought to the stable polymerization reaction condition in the production link, and the production fault is caused by the fluctuation of the polymerization condition under a certain condition, so that the probability of the occurrence of polypropylene production accidents is increased; therefore, the technical scheme of the invention improves the feeding method of the propylene polymerization catalyst, and the propylene polymerization catalyst and the solvent are uniformly mixed to obtain the catalyst premix; then, the catalyst premixed liquid is continuously stirred in the metering tank, the conveying pipeline and the buffer tank to keep the premixed liquid in a state of uniform components, and meanwhile, the temperature and pressure conditions of the buffer tank are controlled to be consistent with the process conditions of the first procedure of the polymerization reactor, so that the influence of catalyst feeding on the polymerization reaction process conditions is reduced, the stable control of the polymerization reaction conditions is realized, and the molecular structure and the performance of a polymerization product are controlled.
The catalyst premixing and the feeding mode of the premixed liquid under the continuous stirring can be carried out by adopting a specially arranged feeding system of the propylene polymerization catalyst.
The catalyst feed system comprises: the mixing tank is provided with a stirrer and is used for uniformly mixing the propylene polymerization catalyst and the solvent to obtain a catalyst premix; a metering tank, wherein the inlet of the metering tank is connected with the outlet of the batching tank; the metering tank is provided with a stirrer and is used for continuously keeping the components of the catalyst premixed liquid uniform; the inlet of the diaphragm metering pump is connected with the outlet of the metering tank and is used for metering the catalyst premixed liquid; the inlet of the buffer tank is connected with the outlet of the diaphragm metering pump, and the outlet of the buffer tank is connected with the polymerization reactor; a stirrer, a temperature controller and a pressure regulator are arranged in the buffer tank; the stirrer is used for continuously keeping the components of the catalyst premix uniform; the temperature controller and the pressure regulator are respectively used for regulating the temperature of the catalyst premixed liquid and the pressure in the buffer tank; and the stirrer with a pipeline structure is arranged on a conveying pipeline connected between the diaphragm metering pump and the buffer tank and is used for continuously keeping the components of the catalyst premixed liquid uniform in the conveying process.
Pipeline structure's agitator, its agitating unit is including running through the (mixing) shaft that sets up in the hybrid pipeline, demountable installation has impeller on the (mixing) shaft, the one end of (mixing) shaft stretches out hybrid pipeline is connected with drive arrangement. The two mixing pipelines are longitudinally arranged in parallel, the bottom ends of the two mixing pipelines are respectively provided with an expansion pipe fitting, and a communication elbow is arranged between the bottom ends of the two expansion pipe fittings; the pipe diameter of the expansion pipe fitting is larger than the pipe diameters of the mixing pipeline and the communication elbow. The driving device comprises a driving motor, and the driving motor is installed above the mixing pipeline through a support.
The feeding system can be suitable for feeding the propylene polymerization catalyst premix, and can also be suitable for controlling uniform feeding of similar suspension.
Preferably, the metering tanks include at least two. Preferably, the metering tanks are connected in parallel. The metering tanks at least comprise two metering tanks, and different metering tanks are connected in parallel. This connection ensures that the suspension of the catalyst components is introduced into the polymerization reactor in a continuous operation.
Preferably, a protective valve is arranged between the metering tank and the diaphragm metering pump. The metering tank and the diaphragm metering pump can be provided with a protection valve, the structural design can isolate the catalyst suspension from being in contact with the diaphragm metering pump for a long time to influence the metering precision and the service life of the metering pump, and the polymerization reaction can be prevented from being influenced by misoperation in production.
Preferably, the stroke of the diaphragm metering pump is adjustable. The stroke of the diaphragm metering pump can be flexibly adjusted according to actual production requirements.
Preferably, the pipeline structure is provided with a plurality of stirrers; the distance between the stirrers of two adjacent pipeline structures is less than 2m. A plurality of stirrers with pipeline structures are arranged on the conveying pipeline of the feeding system according to the length of the pipeline; in order to ensure the effect of continuous stirring, the distance between the two adjacent pipe structures can be adjusted according to the sedimentation property of the suspension and the length of the pipeline, and the distance between the two adjacent pipe structures is smaller than 2m.
The propylene polymerization catalyst comprises a main catalyst and a cocatalyst; wherein, the chemical structural formula of the main catalyst is shown as the following formula:
in the above formula, R 1 And R 2 Each independently selected from one of C1-C20 alkyl, C3-C20 cycloalkyl and C6-C20 aryl; r 3 And R 4 The two are the same or different and are respectively and independently selected from one of hydrogen atoms, C1-C20 alkyl, C3-C20 naphthenic bases and C6-C20 aryl; x is selected from Cl, br, methyl or ethyl; m is selected from titanium, zirconium, hafnium, vanadium, rhodium, iron, nickel, cobalt, neodymium, palladium or yttrium; the cocatalyst comprises an organometallic aluminium compound; the mass ratio of the cocatalyst to the main catalyst is 200-800.
The chemical structural formula of the main catalyst is that a plurality of alkyl substituents are connected on a full heterocyclic ring; the full heterocyclic main ring structure consists of three heteroatoms of Si, N and a transition metal atom M selected from titanium, zirconium, hafnium, vanadium, rhodium, iron, nickel, cobalt, neodymium, palladium or yttrium, and the catalyst with the structure can effectively catalyze copolymerization reaction of ethylene and other alpha-olefins, copolymerization reaction of ethylene and polar alkene monomers, copolymerization reaction of propylene and other alpha-olefins and copolymerization reaction of propylene and polar alkene monomers.
The main catalyst with the structure can be directly matched with a cocatalyst to catalyze olefin polymerization, and can also be matched with the cocatalyst for use after being loaded, and the specific mode can be determined according to actual requirements.
Substituents are respectively connected to three heteroatoms of the main ring structure; the substituents are independently selected from each other and are not limited to each other. In general, the R is 1 And R 2 Each independently selected from one of C1-C20 alkyl, C3-C20 cycloalkyl and C6-C20 aryl; the R is 3 And R 4 Each independently selected from one of hydrogen atom, C1-C20 alkyl, C3-C20 naphthenic base and C6-C20 aryl.
The technical scheme of the invention adopts the non-metallocene catalyst as the main catalyst, the main structure of the non-metallocene catalyst is a complex containing more heteroatoms, and compared with a complex containing only a single heteroatom (such as oxygen, nitrogen and the like), the non-metallocene catalyst has more variability on the structure and has larger adjustment space in the aspects of adjusting the structure and the performance of a polymer; for example, when a certain amount of higher α -olefin (e.g., 1-octene, etc.) is inserted into the molecular chain of polyolefin to prepare a block copolymer, the structure and properties of the polyolefin will change significantly, which not only can make the density of the polymer lower than that of the conventional polyolefin, but also can make the glass transition temperature lower, and has good low temperature resistance, and good dispersibility, weatherability, flexibility, and processability. In addition, the coordination atoms of the main catalyst are nitrogen, nitrogen and silicon, the oxygen affinity of the central metal atom M is weaker, and the structure can easily realize the copolymerization of olefin and polar monomer, so that the functional polyolefin material with excellent performance is synthesized. Meanwhile, the main catalyst has the advantages of high polymerization activity, good particle form, narrow particle size distribution and the like. The main catalyst is very suitable for the gas-phase polymerization process and the bulk polymerization process of propylene, and is particularly suitable for the gas-phase polymerization process.
In principle, the non-metallocene catalyst can be selected as the main catalyst for polymerization, and the main catalyst defined above is preferably used. The above-mentioned main catalyst is also the result of previous research by this research team. The preparation method is shown in CN201611257991.7.
In the propylene polymerization catalyst used in the present invention, the cocatalyst can be selected from organometallic aluminum compounds; further, the organometallic aluminum compound can be selected from alkyl aluminum or alkyl aluminoxane which is a hydrolysate of alkyl aluminum; further, the cocatalyst is selected from at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum or methylaluminoxane.
When the main catalyst and the cocatalyst are used in a certain proportion, the main catalyst and the cocatalyst can effectively catalyze propylene homopolymerization, propylene and ethylene copolymerization, acrylonitrile homopolymerization and propylene and acrylonitrile copolymerization to obtain a propylene copolymer with excellent comprehensive performance and high added value.
In the technical scheme of the invention, the main catalyst and the cocatalyst are matched with each other for catalytic reaction, the main catalyst and the cocatalyst can be directly matched for catalyzing olefin polymerization, and the main catalyst can also be used in combination with the cocatalyst after being pre-loaded. The loading mode of the main catalyst is not particularly limited, and the loading mode in the prior art can be selected.
Preferably, the solvent is selected from at least one of n-hexane, heptane or toluene.
The solvents include those used for premixing the catalyst and those used for solution polymerization. Solution polymerization is a process in which monomers and a catalyst are dissolved in an appropriate solvent to carry out polymerization. The solvent selected is typically an organic solvent, and may also be water, depending on the nature of the monomer, initiator or catalyst and the polymer being produced and the use of the solution of the polymer being produced. Common organic solvents include alcohols, esters, ketones, aromatic hydrocarbons (benzene, toluene), and the like; in addition, aliphatic hydrocarbons, halogenated hydrocarbons, cycloalkanes, and the like are also useful. In the selection of the solvent, the following factors are considered: 1) The influence of the solvent on the polymerization activity is taken into consideration. The solvent is often not absolutely inert, it has an induced decomposition effect on the initiator, and the chain radicals also have a chain transfer reaction with the solvent. Both of these effects may affect the rate of polymerization and the molecular weight. The influence of the solvent is larger in ionic polymerization, and the polarity of the solvent has obvious influence on the existence form and activity of active ion pairs, polymerization reaction rate, polymerization degree, molecular weight and distribution thereof and chain microstructure. For copolymerization reactions, especially ionic copolymerization, the polarity of the solvent can affect the reactivity ratio of the monomers, and further affect the copolymerization behavior, such as copolymerization composition, sequence distribution and the like. Therefore, the solvent should be carefully selected. 2) Influence of the solvent on the solubility properties and gel effect of the polymer. When a good solvent is selected, homogeneous polymerization is carried out, if the concentration of the monomer is not high, the gel effect probably does not occur, and the normal kinetic law of free radical polymerization is followed. When the precipitant is used, precipitation polymerization may occur, and the gel effect is significant. The influence of the poor solvent is between the two, and the influence depth is determined according to the quality and concentration of the solvent. When the gel effect is achieved, the reaction is automatically accelerated, and the molecular weight is increased. When chain transfer occurs simultaneously with the gel effect, the molecular weight distribution will be determined by the depth of influence of these two opposing factors. In order to ensure that the polymer system is homogeneous in the reaction process, the selected solvent has good solubility for an initiator or a catalyst, a monomer and a polymer. This is beneficial to reducing viscosity, slowing down gel effect and leading out polymerization reaction heat. If necessary, a mixed solvent may be used. Meanwhile, factors such as good economy, easy recovery, convenient re-refining, no toxicity, easy commercial availability, low price, convenient transportation and storage and the like need to be considered at the same time. The technical scheme of the invention comprehensively considers the factors and combines the requirements of the adopted catalyst system to obtain better effect when the polymerization reaction is carried out under the anhydrous and oxygen-free conditions, so that the solvent in the invention is preferably at least one of normal hexane, heptane or toluene.
The polymerization system has lower viscosity than bulk polymerization, easier mixing and heat dissipation, easier control of production operation and temperature, and can also utilize evaporation of solvent to remove the heat of polymerization.
When the copolymerization adopts a bulk polymerization method, the solvent is adopted only when the catalyst is dissolved.
As described above, the above-mentioned polymerization process is provided with a step of determining whether or not the set conditions are met, and if it is determined that the polymerization reaction has reached the set conditions, the polymerization reaction needs to be terminated, and at this time, a chain terminator needs to be added to the reaction system to terminate the reaction.
Preferably, the first polymerization further comprises adding a first auxiliary agent; the second polymerization further comprises adding a second aid; the first auxiliary agent and the second auxiliary agent both comprise a chain terminator; the chain terminator is ethanol solution of hydrochloric acid. The volume concentration of the ethanol solution of the hydrochloric acid is 5-15%.
The first auxiliary agent and the second auxiliary agent may be designed and adjusted according to the requirements of the target polymer, and are not particularly limited herein.
Since solution polymerization itself has problems such as environmental problems, solution polymerization is industrially employed only when it is difficult to employ other polymerization methods or when a polymer solution is directly used. The technical scheme of the invention also follows the principle.
The technical scheme of the invention aims to prepare the high value-added propylene copolymer with excellent comprehensive performance, and the adopted monomers are limited as follows: the first olefin monomer is selected from propylene; or a mixture of propylene and ethylene. Wherein the mol content of the propylene in the mixture is more than or equal to 96 percent.
In the first polymerization stage, the first olefin monomer is a mixture of ethylene and propylene or only propylene, and then the ethylene or the propylene is self-polymerized or the ethylene and the propylene are copolymerized; when the reaction conditions are switched to the second polymerization, acrylonitrile units are connected at two ends of the molecular chain of the ethylene polymer or two ends of the molecular chain of the propylene polymer for polymerization; when the reaction conditions are switched to the first polymerization, the two ends of the acrylonitrile unit are connected to carry out polymerization; and the structures of the propylene unit or the ethylene unit and the acrylonitrile unit are alternately connected with ethylene molecules or propylene molecules, and the ethylene molecules or the propylene molecules are sequentially subjected to cyclic polymerization reaction until the polymerization reaction is completed according to the set polymerization reaction conditions, and a chain terminator is added to finish the reaction.
The catalyst system has high catalytic activity when being used for copolymerizing ethylene, propylene and acrylonitrile, and can obtain a propylene copolymer with excellent comprehensive performance and high added value.
When the condition of finishing the polymerization reaction is judged to be reached, a chain terminator can be added through an inlet of the first auxiliary agent or the second auxiliary agent to stop the reaction, the chain terminator is a coordination polar compound, and the technical scheme of the invention adopts an ethanol solution of hydrochloric acid to stop the reaction.
The polymer slurry or solution may be withdrawn from the first polymerisation reactor; the effluent includes polymer and other components that need to be separated and recovered. The separation of the polymer can be carried out by conventional separation means, for example, the polymer can be recovered from the effluent by means of coalescence with a non-solvent or the like.
Preferably, the reaction temperature and reaction pressure of the first polymerization condition and the second polymerization condition are the same or different.
The first polymerization conditions are: the reaction temperature is 40-75 ℃, and the reaction pressure is 0.5-3.0 Mpa; further, the reaction temperature is preferably 40-45 ℃, 45-50 ℃, 50-55 ℃, 55-60 ℃, 60-65 ℃, 65-70 ℃ and 70-75 ℃; the reaction pressure is preferably 0.5 to 1.0Mpa,1.0 to 1.5Mpa,1.5 to 2.0Mpa,2.0 to 2.5Mpa and 2.5 to 3.0Mpa.
The second polymerization conditions are: the reaction temperature is 60-90 ℃, and the reaction pressure is 2.0-4.0 Mpa. Further, the reaction temperature is preferably 60-65 ℃, 65-70 ℃, 70-75 ℃, 75-80 ℃, 80-85 ℃ and 85-90 ℃; the reaction pressure is preferably 2.0-2.5Mpa, 2.5-3.0Mpa, 3.0-3.5Mpa and 3.5-4.0 Mpa.
The polymerization reaction is required to be carried out in an oxygen-free or low-oxygen environment. Preferably, both the first polymerization and the second polymerization are carried out in an inert gas atmosphere. The inert gas atmosphere may be selected from nitrogen, or may be adjusted according to actual conditions.
The amount and concentration of the catalyst for the first polymerization and the second polymerization may be the same or different, and may be specifically designed according to the requirements of the target product and the properties of the olefin monomer, and are not specifically limited herein.
The specific reaction time of the first polymerization and the second polymerization can be specifically designed according to the requirements of the target product and the properties of the olefin monomer, and is not specifically limited herein.
The invention also provides an application of the propylene copolymer.
The molecular structure of the propylene copolymer can be designed according to the process requirements, the acrylonitrile copolymerization component modifies the performance of the ethylene polymer or the propylene polymer in a mode of being connected into a molecular main chain, on one hand, the effective control of the molecular structure is ensured, namely, the molecular structure can be designed, on the other hand, the chemical modification mode also avoids the technical defects existing in the blending modification or reactor blending modification in the prior art, so that technical personnel can design a polymer product according to the target expectation and adjust the structure of the polymer molecule through the control of process conditions, and the propylene copolymer with excellent comprehensive performance and high added value is obtained.
The invention also provides a compatilizer which comprises the propylene copolymer and is applied to polyacrylonitrile and polypropylene blends to improve the compatibility of the polyacrylonitrile and polypropylene blends.
The compatibility detection is that polypropylene and polyacrylonitrile are prepared into a blend according to a certain proportion, and then the phase state distribution of the blend is observed by an electron microscope.
The invention also provides an adhesive which comprises the propylene copolymer and is applied to the adhesion of a polypropylene material and a polar polypropylene material so as to improve the adhesion.
The adhesive force detection is to coat the adhesive on the surface of the metal base material, and measure the peel strength of the metal base material after drying.
The invention also provides a light aging resistant polypropylene resin for outdoor products, which comprises the propylene copolymer.
And the light aging property detection is to put the material in an artificial aging box for accelerated aging, measure the change of tensile strength before and after aging and calculate the strength reduction rate.
The invention also provides an antistatic polypropylene resin, which comprises the propylene copolymer.
The antistatic property is measured by measuring the surface resistivity of the material.
By way of specific examplesTo be more specific, the performance test of the propylene copolymer prepared in each example is performed by using a detection method which is conventional in the art. The preparation method of the main catalyst is shown in CN201611257991.7. In the following examples R is directly used 1 、R 2 、R 3 、R 4 M and X define the structure of the procatalyst.
Example 1
The main catalyst adopts the chemical structural formula (II), wherein R 1 = phenyl, R 2 = phenyl, R 3 = phenyl, R 4 = phenyl, M is titanium, X is Cl, amount 5mg; the cocatalyst adopts methylaluminoxane, and the dosage is 2g; the organic solvent adopts toluene, 200ml; the first olefin monomer is propylene; the second olefin monomer is acrylonitrile; the first polymerization conditions were as follows: under nitrogen environment, the polymerization temperature is 40 ℃, the polymerization pressure is 3Mpa, and the polymerization time is 30min each time; the second polymerization conditions were as follows: in a nitrogen environment, the polymerization temperature is 70 ℃, the polymerization pressure is 2Mpa, and the polymerization time is 10min each time; the cycle was alternated 3 times. The specific operation steps are as follows:
A. dissolving a main catalyst and a cocatalyst in a toluene solvent, uniformly mixing, and continuously stirring for later use;
B. adding a toluene solvent into a polymerization reaction vessel, and controlling a first polymerization condition; introducing a first olefin monomer into a polymerization reactor at the flow rate of 2g/min, dropwise adding a catalyst premixed solution into the polymerization reactor under the condition of continuous stirring, and polymerizing in the polymerization reactor under the stirring state;
C. controlling a second polymerization condition, dropwise adding 2g of a second olefin monomer into the reaction mixture, and dropwise adding the catalyst premixed solution into a polymerization reactor under the condition of continuous stirring, wherein the polymerization reactor carries out polymerization under the stirring state;
D. controlling a first polymerization condition, introducing a first olefin monomer into the reaction mixture at a flow rate of 2g/min, dropwise adding the catalyst premix into a polymerization reactor under the condition of continuous stirring, and polymerizing the polymerization reactor under the stirring state;
E. circularly executing the step C and the step D;
F. the reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed with ethanol 3 times, and then vacuum-dried at 50 ℃ for 24 hours before performance examination.
The performance of the propylene copolymer product prepared in the example was tested, wherein the content and access position of acrylonitrile units were measured by 13C nuclear magnetic resonance, and the results showed that the polymerization sequence of acrylonitrile units in the copolymer was mainly in the middle of the main chain, only a small amount of cyano units were located at the chain end, and the molar percentage of the acrylonitrile units accessed was 1.86%; the weight average molecular weight of the copolymer was measured by gel chromatography and found to be 490000; the melt index was measured according to ASTM D1238 as 19g/10min; the commercially available polypropylene, the commercially available polyacrylonitrile and the copolymer of this example were mixed in a 45%:45%:10 percent of the mixture is melted and mixed to prepare a blend, and the phase state distribution of the blend is observed by an electron microscope, so that the blend is found to be uniformly distributed and has good compatibility; the copolymer sample was placed in an artificial accelerated aging oven for accelerated aging for one month, the change in tensile strength before and after aging was measured, and the strength decrease rate was calculated to be 19.3%.
Example 2
The polymerization process was the same as in example 1. The main catalyst adopts the chemical structural formula, wherein R 1 = benzyl, R 2 = methyl, R 3 = benzyl, R 4 = benzyl, M is zirconium, X is Cl, amount 7mg; the cocatalyst adopts triethyl aluminum, and the dosage is 5.6g; the organic solvent adopts toluene, 200ml; the first olefin monomer is propylene; the second olefin monomer is acrylonitrile; the first polymerization conditions were as follows: under the nitrogen environment, the polymerization temperature is 60 ℃, the polymerization pressure is 2Mpa, and the polymerization time is 25min each time; the second polymerization conditions were as follows: under nitrogen environment, the polymerization temperature is 60 ℃, the polymerization pressure is 3Mpa, and each polymerization time is 8min; the cycle was alternated 4 times.
The propylene copolymer product prepared in the example is subjected to performance detection, and the molar percentage content of acrylonitrile units in the copolymer is 2.51%; the weight average molecular weight of the copolymer was measured by gel chromatography and found to be 370000; the melt index is 21g/10min according to ASTM D1238; the strength reduction rate of the copolymer sample after artificial accelerated aging was calculated to be 14.8%.
Example 3
The polymerization process was the same as in example 1. The main catalyst adopts the chemical structural formula, wherein R 1 = cyclohexyl, R 2 = methyl, R 3 = cyclohexyl, R 4 = cyclohexyl, M is yttrium, X is Cl, amount 6mg; the cocatalyst adopts trimethylaluminum, and the dosage is 1.2g; the organic solvent adopts n-hexane, 200ml; the first olefin monomer is propylene; the second olefin monomer is acrylonitrile; the first polymerization conditions were as follows: under nitrogen environment, the polymerization temperature is 50 ℃, the polymerization pressure is 2.5Mpa, and each polymerization time is 30min; the second polymerization conditions were as follows: under nitrogen environment, the polymerization temperature is 80 ℃, the polymerization pressure is 3Mpa, and each polymerization time is 8min; the cycle was alternated 5 times.
The propylene copolymer product prepared in the example is subjected to performance detection, and the molar percentage content of acrylonitrile units in the copolymer is 2.23%; the weight average molecular weight of the copolymer was measured by gel chromatography and found to be 620000; the melt index is 15g/10min according to ASTM D1238; the strength reduction rate of the copolymer sample after artificial accelerated aging was calculated to be 15.1%.
Example 4
The polymerization process was the same as in example 1. The main catalyst adopts the chemical structural formula, wherein R 1 = phenyl, R 2 = phenyl, R 3 = phenyl, R 4 = cyclopentyl, M is neodymium, X is Cl, amount 8mg; the cocatalyst adopts tri-n-hexyl aluminum, and the dosage is 6g; the organic solvent adopts heptane, 200ml; the first olefin monomer is propylene 96% and ethylene 4%; the second olefin monomer is acrylonitrile; the first polymerization conditions were as follows: under nitrogen environment, the polymerization temperature is 70 ℃, the polymerization pressure is 1.5Mpa, and each polymerization time is 20min; the second polymerization conditions were as follows: under nitrogen environment, the polymerization temperature is 90 ℃, the polymerization pressure is 4Mpa, and the polymerization time is 5min each time; the cycle was alternated 2 times.
The propylene copolymer product prepared in the example is subjected to performance detection, and the molar percentage content of acrylonitrile units in the copolymer is 2.62%; the weight average molecular weight of the copolymer was measured by gel chromatography and found to be 160000; the melt index is 32g/10min according to ASTM D1238; the strength reduction rate of the copolymer sample after artificial accelerated aging was calculated to be 13.2%.
Example 5
The polymerization process was the same as in example 1. The main catalyst adopts the chemical structural formula, wherein R 1 = cyclopentyl, R 2 = methyl, R 3 = phenyl, R 4 = phenyl, M rhodium, X Cl, amount 5mg; triisobutyl aluminum is adopted as a cocatalyst, and the using amount is 3g; the organic solvent adopts toluene, 200ml; the first olefin monomer is propylene; the second olefin monomer is acrylonitrile; the first polymerization conditions were as follows: in a nitrogen environment, the polymerization temperature is 75 ℃, the polymerization pressure is 0.5Mpa, and the polymerization time is 20min each time; the second polymerization conditions were as follows: in a nitrogen environment, the polymerization temperature is 85 ℃, the polymerization pressure is 3Mpa, and the polymerization time is 10min each time; the cycle was alternated 4 times.
The propylene copolymer product prepared in the example is subjected to performance detection, and the molar percentage content of acrylonitrile units in the copolymer is 3.11%; the weight average molecular weight of the copolymer was measured by gel chromatography and found to be 420000; the melt index is 20g/10min according to ASTM D1238; the strength reduction rate of the copolymer sample after artificial accelerated aging was calculated to be 11.7%.
Example 6
The polymerization process was the same as in example 1. The main catalyst adopts the chemical structural formula, wherein R 1 = ethyl, R 2 = ethyl, R 3 = phenyl, R 4 = phenyl, M is vanadium, X is Br, dosage is 7mg; triisobutyl aluminum is adopted as a cocatalyst, and the using amount is 5g; the organic solvent adopts toluene, 200ml; the first olefin monomer is propylene; the second olefin monomer is acrylonitrile; the first polymerization conditions were as follows: under nitrogen environment, the polymerization temperature is 65 ℃, the polymerization pressure is 1Mpa, and the polymerization time is 30min each time; the second polymerization conditions were as follows: the polymerization temperature is 75 ℃ and the polymerization pressure is 3M under a nitrogen environmentpa, polymerization time 5min each; the cycle was alternated 3 times.
The propylene copolymer product prepared in the example is subjected to performance detection, and the molar percentage content of acrylonitrile units in the copolymer is 1.89%; the weight average molecular weight of the copolymer was measured by gel chromatography and found to be 350000; the melt index is 21g/10min according to ASTM D1238; the strength reduction rate of the copolymer sample after artificial accelerated aging was calculated to be 18.2%.
Example 7
The polymerization process was the same as in example 1. The main catalyst adopts the chemical structural formula, wherein R 1 = isopropyl, R 2 = isopropyl, R 3 = phenyl, R 4 = methyl, M is nickel, X is Cl, amount 6mg; the cocatalyst adopts methylaluminoxane, and the dosage is 4.8g; the organic solvent adopts toluene, 200ml; the first olefin monomer is propylene; the second olefin monomer is acrylonitrile; the first polymerization conditions were as follows: under nitrogen atmosphere, at 45 deg.C and 2.5Mpa, each time for 10min; the second polymerization conditions were as follows: under nitrogen atmosphere, at 65 deg.C and 3Mpa for 5min; the cycle was alternated 3 times.
The propylene copolymer product prepared in the example is subjected to performance detection, and the molar percentage content of acrylonitrile units in the copolymer is 4.97%; the weight average molecular weight of the copolymer was measured by gel chromatography, and found 140000; the melt index is 35g/10min according to ASTM D1238; the strength reduction rate of the copolymer sample after artificial accelerated aging was calculated to be 4.7%.
Example 8
The polymerization process was the same as in example 1. The main catalyst adopts the chemical structural formula, wherein R 1 =2,6-dimethylphenyl, R 2 =2,6-dimethylphenyl, R 3 =2,6-dimethylphenyl, R 4 = methyl, M is cobalt, X is Cl, amount 6mg; the cocatalyst adopts methylaluminoxane with the dosage of 4.8g; the organic solvent adopts toluene, 200ml; the first olefin monomer is propylene; the second olefin monomer is acrylonitrile; the first polymerization conditions were as follows:under nitrogen environment, the polymerization temperature is 60 ℃, the polymerization pressure is 2Mpa, and each polymerization time is 15min; the second polymerization conditions were as follows: under nitrogen environment, the polymerization temperature is 70 ℃, the polymerization pressure is 4Mpa, and the polymerization time is 5min each time; the cycle was alternated 3 times.
The propylene copolymer product prepared in the example is subjected to performance detection, and the molar percentage content of acrylonitrile units in the copolymer is 3.81%; the weight average molecular weight of the copolymer was measured by gel chromatography and found to be 210000; the melt index is 29g/10min according to ASTM D1238; the strength reduction rate of the copolymer sample after artificial accelerated aging was calculated to be 8.3%.
Example 9
The polymerization process was the same as in example 1. The main catalyst adopts the chemical structural formula, wherein R 1 =2,6-dimethylphenyl, R 2 =2,6-dimethylphenyl, R 3 =2,6-dimethylphenyl, R 4 = methyl, M is cobalt, X is Cl, amount 6mg; the cocatalyst adopts methylaluminoxane, and the dosage is 4.8g; the organic solvent adopts toluene, 200ml; the first olefin monomer is acrylonitrile; the second olefin monomer is propylene; the first polymerization conditions were as follows: under nitrogen environment, the polymerization temperature is 70 ℃, the polymerization pressure is 4Mpa, and the polymerization time is 5min each time; alternately cycling for 3 times; the second polymerization conditions were as follows: the polymerization temperature is 60 ℃, the polymerization pressure is 2Mpa, and each polymerization time is 15min.
The propylene copolymer product prepared in the example is subjected to performance detection, and the molar percentage content of acrylonitrile units in the copolymer is 6.58%; the weight average molecular weight of the copolymer was measured by gel chromatography and found 163000; the melt index is 30.5g/10min according to ASTM D1238; the strength reduction rate of the copolymer sample after artificial accelerated aging was calculated to be 7.6%.
Comparative example 1
The kind and amount of the main catalyst, the kind and amount of the cocatalyst, the kind and amount of the organic solvent, and the kind and amount of the first olefin monomer and the second olefin monomer used are the same as those of example 3; the polymerization conditions were as follows: the polymerization temperature is 50 ℃, the polymerization pressure is 2.5Mpa, and each polymerization time is 220min.
Comparative example 2
The kind and amount of the main catalyst, the kind and amount of the cocatalyst, the kind and amount of the organic solvent, and the kind and amount of the first olefin monomer and the second olefin monomer used are the same as those of example 3; the polymerization conditions were as follows: the polymerization temperature is 80 ℃ and the polymerization pressure is 3Mpa under a nitrogen environment, and the polymerization time is 220min each time.
The above embodiments 1 to 9 are only specific examples for realizing the technical solution of the present invention, and through the above embodiments, the present invention respectively uses propylene or propylene containing a small amount of ethylene as a first olefin monomer, uses an acrylonitrile monomer as a comonomer to copolymerize under the alternative process conditions proposed by the present invention, and controls the polymerization reaction to apply different reaction conditions in different processes, so as to switch the polymerization process under different reaction conditions according to the process design, thereby controlling the molecular structure of the polymer to grow according to the designed molecular chain. Meanwhile, according to the technical scheme of the invention, by controlling the feeding method of the catalyst, the catalyst components introduced into the polymerization reactor are uniform, the temperature and the pressure of the catalyst components are consistent with those of the polymerization reactor, the influence of the feeding process of the catalyst on the polymerization reaction is minimized, the process conditions of the polymerization reaction are controlled, the high-performance polyolefin with a designable molecular structure is prepared, the uniformity and the comprehensive performance of the molecular structure of the product are improved, meanwhile, the blockage of a feeding pipeline can be avoided, and the production efficiency is improved.
The comparative examples 1 and 2 above employed the same charge amount and reaction time as in example 3, and only employed no alternate copolymerization process route, and it can be seen from the results of the propylene copolymer obtained, that the polymerization sequence of the acrylonitrile unit and the polymerization sequence of the propylene unit in the propylene copolymer could not grow according to the designed molecular structure when copolymerized under a single condition, and due to the large difference in reactivity ratio between the two, the product formed was a simple combination of the polymerization sequence of the long-stage propylene unit and the polymerization sequence of the long-stage acrylonitrile unit, and it was difficult to form a molecular structure in which the polymerization sequence of the propylene unit and the polymerization sequence of the acrylonitrile unit alternately appeared; therefore, the technical scheme of the invention can reasonably control the time for the first olefin monomer and the second olefin monomer to be connected into the polymer molecular chain and the molecular sequence arrangement state by adopting an alternate copolymerization process route, and can obtain the copolymer with a designable molecular structure.
Furthermore, the chain structure and sequence structure of the copolymer will directly affect various properties of the copolymer when used as a polymer material, such as mechanical properties, dielectric properties, thermal properties, etc., and will also directly affect the selection of molding conditions. The invention determines the chain end length and the chain structure of the macromolecule through gel chromatography, distinguishes the characteristic 'fingerprint' generated by the variation of the nuclear magnetic moment energy level of the atomic nucleus in the molecule through the nuclear magnetic resonance method, and obtains the structural information of the molecule; and comprehensively analyzing and deducing the sequence structure of the polymer chain through the obtained information. Through comparative analysis, the molecular chain sequences of the embodiment 3, the comparative example 1 and the comparative example 2 can be judged that the sequence of the molecular chain structure of the polymer prepared by the technical scheme of the invention connected to the molecular chain is stably controlled, and when the letter A represents a first olefin unit and the letter B represents a second olefin unit, the molecular chain structure of the polymer is basically presented as a block type and belongs to a special gradient sequence structure, which is schematically shown as AAAAAAABBBAAABBBB.; in the comparative example, the technical scheme of the invention is not adopted to alternatively feed the comonomer, and after several monomers enter a reaction system together, a polymer with an unstable structure is randomly generated mainly through reactivity ratio differences of several olefin monomers, the molecular structure of the polymer is not controlled, and the performance of the polymer is also unstable.
Further, for the propylene copolymer of example 7 of the present inventionThe sheet was produced, and the surface resistivity thereof was measured, and it was found to be 5.6X 10 8 Omega, the antistatic performance is good, and the molecular structure is connected into the molecular main chain in the form of chemical structure, so that the antistatic performance of the polymer is not influenced by the migration of groups along with time.
Further, the propylene copolymer of example 7 of the present invention was dissolved and coated on a metal substrate, and the peel strength was measured after drying, and as a result, 25.3N/10mm showed excellent adhesion properties, and the molecular structure was grafted into the molecular main chain in the form of a chemical structure, and the group migration did not occur with time to affect the adhesion of the polymer.
The present invention is capable of other embodiments, and various changes and modifications can be made by one skilled in the art without departing from the spirit and scope of the invention.
Claims (22)
1. A propylene copolymer comprising in its molecular backbone a polymerized sequence of propylene units and a polymerized sequence of acrylonitrile units, said polymerized sequences of propylene units alternating with said polymerized sequence of acrylonitrile units and having the formula:
wherein m, m ', n and n' are positive integers, m: n is 20 to 100: n' is 20 to 100.
2. Propylene copolymer according to claim 1, characterized in that the polymerization sequences of the acrylonitrile units comprise polymerization sequences located in the middle of the molecular chain and polymerization sequences located at the ends of the molecular chain; wherein the content of the polymerization sequence located in the middle of the molecular chain is greater than the content of the polymerization sequence located at the end of the molecular chain.
3. The propylene copolymer according to claim 1, wherein the percentage of the acrylonitrile units in the propylene copolymer is from 1.0 to 5.0% in terms of mole ratio.
4. A propylene copolymer according to claim 1 or 2, characterized in that the weight average molecular weight of the propylene copolymer is from 50000 to 1000000.
5. The propylene copolymer of claim 3 having a melt index of 10 to 40g/10min as measured according to ASTM D1238.
6. A process for the preparation of a propylene copolymer as claimed in any of claims 1 to 5, comprising the steps of:
(1) In the presence of a propylene polymerization catalyst, introducing a first olefin monomer into a polymerization reactor, and polymerizing under first polymerization conditions;
(2) Introducing a second olefin monomer into the reaction mixture of the step (1) in the presence of a propylene polymerization catalyst, and polymerizing under second polymerization conditions;
(3) Introducing a first olefin monomer into the reaction mixture of the step (2) in the presence of a propylene polymerization catalyst to polymerize the first olefin monomer under first polymerization conditions;
(4) The step 2) and the step 3) are executed and repeated for 2 to 5 times;
(5) Adding a chain terminator to terminate the reaction, and then filtering and washing to obtain the propylene copolymer.
7. The method according to claim 6, wherein in the step (1), the propylene polymerization catalyst is introduced into the polymerization reactor as follows:
(11) Uniformly mixing a propylene polymerization catalyst and a solvent to obtain a catalyst premix;
(12) The catalyst premixed liquid is sequentially metered, conveyed and buffered and then is introduced into a polymerization reactor; wherein the components of the premixed liquid in the metering, conveying and buffering processes are controlled to be uniform, and the pressure in a buffer tank adopted in the buffering process is controlled to be the same as the pressure in the polymerization reactor.
8. The process according to claim 6, wherein the first polymerization conditions and the second polymerization conditions are carried out alternately in a spatial sequence in the same polymerization reactor; two reaction zones with independently controlled reaction conditions are arranged in the polymerization reactor; each reaction zone is provided with a catalyst feed system.
9. The production method according to claim 6, characterized in that the first polymerization conditions and the second polymerization conditions are alternately carried out in a spatial sequence in two serially connected polymerization reactors, respectively; each of the polymerization reactors is provided with a catalyst feed system.
10. The method of claim 7, wherein the metering comprises metering the catalyst premix solution in a metering tank; the metering tank is equipped with a stirring cycle and is metered precisely by a diaphragm metering pump.
11. The method according to claim 7, wherein a pipeline-structured stirrer is provided in the pipeline for the transportation.
12. The method of claim 7, wherein the buffering comprises circulation of the catalyst premix in a buffer tank under agitation and adjustment of the temperature of the premix and the pressure in the buffer tank.
13. The production method according to claim 6, wherein the propylene polymerization catalyst comprises a main catalyst and a cocatalyst; wherein,
the chemical structural formula of the main catalyst is shown as the following formula:
in the formula II, R 1 And R 2 Each independently selected from one of C1-C20 alkyl, C3-C20 cycloalkyl and C6-C20 aryl; r 3 And R 4 The two are the same or different and are respectively and independently selected from one of hydrogen atoms, C1-C20 alkyl, C3-C20 naphthenic bases and C6-C20 aryl; x is selected from Cl, br, methyl or ethyl; m is selected from titanium, zirconium, hafnium, vanadium, rhodium, iron, nickel, cobalt, neodymium, palladium or yttrium;
the cocatalyst comprises an organometallic aluminium compound; preferably, the organometallic aluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum or methylaluminoxane;
the mass ratio of the cocatalyst to the main catalyst is 200-800.
14. The method according to claim 7, wherein the solvent is at least one selected from the group consisting of n-hexane, n-heptane and toluene.
15. The method according to claim 6, wherein the chain terminator is an ethanol solution of hydrochloric acid.
16. The preparation method according to claim 6, wherein the first olefin monomer is one selected from a mixture of propylene and ethylene, and propylene, preferably, the molar content of propylene in the mixture is greater than or equal to 96%; the second olefin monomer is selected from acrylonitrile monomers.
17. The production method according to claim 6, wherein the reaction temperature and the reaction pressure of the first polymerization condition and the second polymerization condition are the same or different; the first polymerization conditions are: the reaction temperature is 40-75 ℃, and the reaction pressure is 0.5-3.0 Mpa; the second polymerization conditions are: the reaction temperature is 60-90 ℃, and the reaction pressure is 2.0-4.0 Mpa.
18. The method of claim 6, wherein the first polymerization condition and the second polymerization condition are both reacted under an inert gas atmosphere.
19. A compatibilizer, characterized in that it comprises the propylene copolymer of any one of claims 1 to 5, used in polyacrylonitrile and polypropylene blends to improve the compatibility thereof.
20. An adhesive comprising a propylene copolymer as claimed in any of claims 1 to 5 for bonding a polypropylene material to a polar polypropylene material to improve the adhesion thereof.
21. A photoaging resistant polypropylene resin for outdoor products, comprising the propylene copolymer of any one of claims 1 to 5.
22. An antistatic polypropylene resin comprising the propylene copolymer according to any one of claims 1 to 5.
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| US4577008A (en) * | 1984-06-27 | 1986-03-18 | The Standard Oil Company | Process for the production of acrylonitrile-propylene copolymers |
| CN101787158A (en) * | 2009-10-10 | 2010-07-28 | 深圳市科聚新材料有限公司 | Directly sprayed polypropylene material and preparation method thereof |
| CN104371060A (en) * | 2013-08-13 | 2015-02-25 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile resin with evenly-distributed copolymerization sequence |
| WO2016210419A1 (en) * | 2015-06-26 | 2016-12-29 | Florida State University Research Foundation, Inc. | Dry process method for producing electrodes for electrochemical devices and electrodes for electrochemical devices |
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| US4577008A (en) * | 1984-06-27 | 1986-03-18 | The Standard Oil Company | Process for the production of acrylonitrile-propylene copolymers |
| CN101787158A (en) * | 2009-10-10 | 2010-07-28 | 深圳市科聚新材料有限公司 | Directly sprayed polypropylene material and preparation method thereof |
| CN104371060A (en) * | 2013-08-13 | 2015-02-25 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile resin with evenly-distributed copolymerization sequence |
| WO2016210419A1 (en) * | 2015-06-26 | 2016-12-29 | Florida State University Research Foundation, Inc. | Dry process method for producing electrodes for electrochemical devices and electrodes for electrochemical devices |
| US20180175366A1 (en) * | 2015-06-26 | 2018-06-21 | Florida State University Research Foundation, Inc. | Dry process method for producing electrodes for electrochemical devices and electrodes for electrochemical devices |
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