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CN117624415A - Olefin polymerization system, method and anti-sticking agent used in same - Google Patents

Olefin polymerization system, method and anti-sticking agent used in same Download PDF

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Publication number
CN117624415A
CN117624415A CN202210971764.XA CN202210971764A CN117624415A CN 117624415 A CN117624415 A CN 117624415A CN 202210971764 A CN202210971764 A CN 202210971764A CN 117624415 A CN117624415 A CN 117624415A
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catalyst
containing compound
polymerization
silane
carbon number
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孟子逸
窦彤彤
李红明
义建军
雷珺宇
黄启谷
袁定坤
张渊
杨威
郭文思
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Petrochina Co Ltd
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

The invention provides an olefin polymerization reaction system, a method and an anti-adhesion agent used by the same, wherein the anti-adhesion agent comprises at least one of an oxygen-containing compound, a nitrogen-containing compound, a sulfur-containing compound, a silicon-containing compound and a phosphorus-containing compound, the general formula of the oxygen-containing compound is shown as a formula I, the general formula of the nitrogen-containing compound is shown as a formula II, the general formula of the sulfur-containing compound is shown as a formula III, the general formula of the silicon-containing compound is shown as a formula IV, the general formula of the phosphorus-containing compound is shown as a formula V or a formula VI,wherein, -R 1 、‑R 2 Is hydrocarbon, and the total carbon number is between 8 and 60; -R 3 、‑R 4 、‑R 5 is-H or alkyl, and the total carbon number is between 8 and 60; -R 6 、‑R 7 is-H or alkyl, and the total carbon number is between 8 and 60; -R 8 、‑R 9 、‑R 10 、‑R 11 Is hydrocarbon or hydrocarbyloxy, the total carbon number is between 8 and 60; -R 12 、‑R 13 、‑R 14 is-H, alkyl or alkoxy, and the total carbon number is 8-60. The invention solves the problems of kettle adhesion, stirrer adhesion, other accessory adhesion or pipe blockage and the like in the olefin polymerization process through the action of the anti-adhesion agent.

Description

Olefin polymerization system, method and anti-sticking agent used in same
Technical Field
The invention belongs to the field of olefin polymerization materials, and particularly relates to an olefin polymerization reaction system, an olefin polymerization reaction method and an anti-sticking agent used by the olefin polymerization reaction system.
Background
The polyolefin includes polyethylene, polypropylene, polyvinyl chloride, polystyrene, and the like. Polyethylene is the simplest general thermoplastic resin and elastomer obtained by polymerization of ethylene monomers under the action of an initiator or a catalyst. The polyethylene products have multiple varieties and brands, and can meet the demands of different fields. Polypropylene is mainly isotactic polypropylene (iPP) and its copolymers. The catalyst for synthesizing polyolefin is synthesized by coordination polymerization mainly using high-efficiency load type Ziegler-Natta catalyst. Another part of coordination polymerization is homo-polymerization or copolymerization of olefins including ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene or norbornene, etc. using metallocene catalysts, constrained geometry metallocene catalysts (CGC) and non-metallocene catalysts, particularly using metallocene catalysts including CGC catalysts, to produce mPE, POE, mPP, COC, EPDM, EPR, POP, PMP, OBC, etc. has found many industrial applications worldwide. The method is also developed in the industrial field of China.
However, a serious problem in the metallocene polyolefin industry in the field of industrial coordination polymerization is that the phenomena of kettle sticking, reactor sticking, stirrer sticking, other accessories sticking or pipe blocking easily occur in the process of synthesizing polyolefin by using a metallocene catalyst, a constrained geometry metallocene catalyst (CGC) and a non-metallocene catalyst, and a supported metallocene catalyst or a supported non-metallocene catalyst. The polyolefin is plastic or elastomer, is easy to attach to the inner wall of a reactor, a stirrer or other accessories, seriously affects mass transfer, heat transfer and transfer quantity, often causes caking and even scorching of products, and is forced to stop and stop production.
In the current coordination polymerization field, the method for solving the problem of kettle adhesion of polyolefin products is limited under the condition of not changing the polymerization process. Patent US20120046426 discloses that the addition of hydrocarbyl/magnesium alkoxide compounds during olefin polymerization is effective in reducing pot sticking. Patent CN105542039a discloses that supported Ziegler-Natta catalysts can catalyze to obtain polymers with good particle morphology, high bulk density, low fines, and do not adhere to the vessel walls. Patent CN108727527a discloses that the novel supported metallocene catalysts also give polyolefin products that are not sticky to the pot.
From the above, the main means adopted in the art to solve the problem of kettle sticking is to develop a new catalyst, and the components with anti-sticking effect in the catalyst are not summarized, so that the universality is poor.
Disclosure of Invention
The invention mainly aims to provide an olefin polymerization reaction system, an olefin polymerization reaction method and an anti-adhesion agent used by the olefin polymerization reaction system, the anti-adhesion agent has universality, can be matched with any catalyst used for olefin polymerization reaction in the prior art, and solves the problems of adhesion of a kettle, an adhesion reactor, an adhesion stirrer, adhesion of other accessories or pipe blockage and the like.
In order to achieve the above object, the present invention provides an anti-sticking agent for an olefin polymerization system, the anti-sticking agent comprising at least one of an oxygen-containing compound having the formula I, a nitrogen-containing compound having the formula II, a sulfur-containing compound having the formula III, a phosphorus-containing compound having the formula IV, and a phosphorus-containing compound having the formula V or VI,
wherein, -R 1 、-R 2 Is hydrocarbon, and the total carbon number is between 8 and 60;
-R 3 、-R 4 、-R 5 is-H or alkyl, and the total carbon number is between 8 and 60;
-R 6 、-R 7 is-H or alkyl, and the total carbon number is between 8 and 60;
-R 8 、-R 9 、-R 10 、-R 11 is hydrocarbon or hydrocarbyloxy, the total carbon number is between 8 and 60;
-R 12 、-R 13 、-R 14 is-H, alkyl or alkoxy, and the total carbon number is 8-60.
The invention relates to an anti-adhesive for an olefin polymerization system, wherein R 1 and-R 2 A total carbon number of between 8 and 30, -R 3 、-R 4 、-R 5 A total carbon number of between 8 and 30, -R 6 、-R 7 A total carbon number of between 8 and 30, -R 8 、-R 9 、-R 10 、-R 11 A total carbon number of between 8 and 30, -R 12 、-R 13 、-R 14 And the total carbon number of (2) is between 8 and 30.
The invention relates to an anti-adhesive for an olefin polymerization reaction system, wherein the oxygen-containing compound is at least one selected from dibutyl ether, dipentyl ether, dihexyl ether, diheptyl ether and diphenyl ether; the silicon-containing compound is at least one selected from methyl dimethoxy cyclohexyl silane, methyl dimethoxy cyclopentyl silane, trimethoxy cyclohexyl silane, trimethoxy cyclopentyloxy silane, trimethoxy cyclohexyloxy silane, ethyl dimethoxy cyclohexyl silane, methyl diethoxy cyclopentyl silane, methyl diethoxy cyclohexyloxy silane, methyl dimethoxy cyclopentyloxy silane, dimethyl ethoxy cyclohexyl silane, dimethyl methoxy cyclopentyl silane, dimethyl ethoxy cyclohexyloxy silane, dimethyl ethoxy cyclopentyloxy silane, cyclohexyl methyl dimethoxy silane and dicyclopentyl dimethoxy silane; the phosphorus-containing compound is at least one selected from tributyl phosphate, tricyclopentyl phosphate, dibutyl phosphite, 2-ethylhexyl phosphate, tributylphosphine, tricyclohexyl phosphine, tri-n-butyl phosphine and trihexyl phosphorus oxide; the sulfur-containing compound is at least one selected from dipentyl disulfide, 1, 9-nonyldithiol, n-dodecyl mercaptan, bis (16-hydroxyhexadecyl) disulfide and dicyclohexyl disulfide; the nitrogen-containing compound is at least one selected from the group consisting of tripentylamine, dihexylamine, dicyclohexylamine, spermine, spermidine, decylamine, 3-propylpiperidine, 4-piperidylpiperidine, (1-cyclopropylpyrrolidin-3-yl) methylamine, N, N, N ', N' -tetramethyl-1, 6-hexamethylenediamine, N-propylcyclohexylamine, N, N-dimethylcyclohexylamine.
In order to achieve the above object, the present invention also provides an olefin polymerization reaction system to which the above-mentioned anti-sticking agent is added.
In order to achieve the above object, the present invention further provides a method for polymerizing olefins, which comprises polymerizing olefins as raw materials under the action of a catalyst and the anti-sticking agent.
The olefin polymerization reaction method provided by the invention, wherein the anti-adhesion agent is added in the preparation process or the preparation process of the catalyst, or the anti-adhesion agent and the catalyst are added in the olefin prepolymerization process.
The invention relates to an olefin polymerization reaction method, wherein the catalyst is a metallocene catalyst, a constrained geometry metallocene catalyst, a non-metallocene catalyst, a supported constrained geometry metallocene catalyst or a supported non-metallocene catalyst.
The olefin polymerization reaction method of the present invention, wherein the polymerization reaction is a solution polymerization reaction, a gas phase polymerization reaction, a liquid phase bulk polymerization reaction, a slurry polymerization reaction, a loop polymerization reaction or a combination polymerization reaction.
The olefin polymerization method of the present invention, wherein the olefin polymerization method comprises the steps of:
step 1, fully contacting the catalyst and the anti-adhesion agent;
step 2, mixing a cocatalyst with the mixture obtained in the step 1;
and 3, carrying out polymerization reaction on the olefin under the action of the mixture obtained in the step 2.
The olefin polymerization reaction method of the invention, wherein the molar ratio of the catalyst to the anti-adhesion agent is 1:0.01-2, and the molar ratio of the catalyst to the cocatalyst is 1:10-1000, calculated by transition metal; the cocatalyst is at least one selected from trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-tert-butylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methoxyaluminum and modified methoxyaluminum.
The invention relates to an olefin polymerization reaction method, wherein the polymerization reaction of olefin is ethylene polymerization reaction, propylene polymerization reaction, copolymerization reaction of ethylene and other organic matters containing carbon-carbon double bonds, copolymerization reaction of propylene and other organic matters containing carbon-carbon double bonds, wherein the other organic matters containing carbon-carbon double bonds are selected from C 2 -C 30 Alpha-olefins, C 6 -C 30 Diene, C 3 -C 100 An oxygen-containing organic substance containing carbon-carbon double bonds,the C is 2 -C 30 The alpha-olefin of (C) is selected from ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, dicyclopentadiene, norbornene or mixtures thereof 3 -C 100 Preferably, the oxygen-containing organic matter containing carbon-carbon double bonds is selected from 7-octen-1-ol, 9-decen-1-ol or a mixture thereof.
The olefin polymerization reaction method of the invention, wherein the temperature of the polymerization reaction is 20-200 ℃, the time is 5-300min, and the gas pressure is 0.05-40MPa.
The invention has the beneficial effects that:
the heteroatom (oxygen, nitrogen, sulfur, silicon and phosphorus) of the anti-adhesive can be contacted with the active site of the catalyst for olefin polymerization, and the electronegativity of the heteroatom changes the charge density distribution of the central transition metal atom of the active site of the catalyst and changes the electronic effect of the active site of the catalyst. In addition, as the heteroatom of the anti-adhesion agent contacts with the active site of the catalyst, the distance between the anti-adhesion agent molecule and the active site of the catalyst is very short, the anti-adhesion agent molecule changes the coordination space of the active site of the catalyst, namely the coordination environment of olefin is changed, so that the content of low-molecular-weight polyolefin obtained by olefin polymerization is reduced, further, polyolefin with higher molecular weight is obtained, the polyolefin product in the polymerization reactor is not sticky, and the problems of adhesion of a kettle, a reactor, a stirrer, other accessories or pipe blockage in the olefin polymerization process are solved.
Drawings
FIG. 1 is a schematic illustration of a pot adhesion of an olefin polymerization system incorporating the anti-adhesion agent of the present invention.
FIG. 2 is a schematic illustration of a pot adhesion without the addition of the anti-adhesion agent of the present invention to an olefin polymerization system.
Detailed Description
The following embodiments are provided by carrying out the embodiments of the present invention on the premise of the embodiments of the present invention, and the detailed implementation process is given, but the scope of the present invention is not limited to the following embodiments, and the following embodiments do not specify specific conditions, structures or experimental methods, and generally follow conventional conditions.
The invention provides an anti-adhesion agent for an olefin polymerization reaction system, which comprises at least one of an oxygen-containing compound, a nitrogen-containing compound, a sulfur-containing compound, a silicon-containing compound and a phosphorus-containing compound, wherein the general formula of the oxygen-containing compound is shown as a formula I, the general formula of the nitrogen-containing compound is shown as a formula II, the general formula of the sulfur-containing compound is shown as a formula III, the general formula of the silicon-containing compound is shown as a formula IV, the general formula of the phosphorus-containing compound is shown as a formula V or a formula VI,
wherein, -R 1 、-R 2 Is hydrocarbon, and the total carbon number is between 8 and 60;
-R 3 、-R 4 、-R 5 is-H or alkyl, and the total carbon number is between 8 and 60;
-R 6 、-R 7 is-H or alkyl, and the total carbon number is between 8 and 60;
-R 8 、-R 9 、-R 10 、-R 11 is hydrocarbon or hydrocarbyloxy, the total carbon number is between 8 and 60;
-R 12 、-R 13 、-R 14 is-H, alkyl or alkoxy, and the total carbon number is 8-60.
The heteroatom (oxygen, nitrogen, sulfur, silicon and phosphorus) of the anti-adhesive can be contacted with the active site of a catalyst for olefin polymerization in the prior art, and the charge density distribution of a central transition metal atom of the active site of the catalyst is changed due to the strong electronegativity of the heteroatom, so that the electron effect of the active site of the catalyst is changed. In addition, since the heteroatom of the anti-adhesion agent contacts with the catalyst active site, the distance between the anti-adhesion agent molecule and the catalyst active site is very short, and the coordination space of the catalyst active site is changed by the anti-adhesion agent molecule. Therefore, the anti-sticking agent can change the coordination environment of olefin, so that the content of low molecular weight polyolefin obtained by olefin polymerization is reduced, and more importantly, the problems of kettle sticking, reactor sticking, stirrer sticking, other accessories sticking or pipe blocking and the like in the olefin polymerization process are solved.
In one embodiment, in the anti-adhesive of the present invention, R 1 and-R 2 The total carbon number of (2) is between 8 and 30, more preferably between 8 and 20, -R 3 、-R 4 、-R 5 The total carbon number of (2) is between 8 and 30, more preferably between 8 and 20, -R 6 、-R 7 The total carbon number of (2) is between 8 and 30, more preferably between 8 and 20, -R 8 、-R 9 、-R 10 、-R 11 The total carbon number of (2) is between 8 and 30, more preferably between 8 and 20, -R 12 、-R 13 、-R 14 And more preferably between 8 and 20.
Wherein the oxygen-containing compound is, for example, ether or oxa-compound, the sulfur-containing compound is, for example, thioether, mercaptan or thia-compound, the nitrogen-containing compound is, for example, amine-type compound, the silicon-containing compound is, for example, silane-type compound, and the phosphorus-containing compound is, for example, phosphine oxide or (phosphorous) phosphate.
In another embodiment, the oxygenate of the present invention is selected from at least one of dibutyl ether, dipentyl ether, dihexyl ether, diheptyl ether, and diphenyl ether; the silicon-containing compound is at least one selected from methyl dimethoxy cyclohexyl silane, methyl dimethoxy cyclopentyl silane, trimethoxy cyclohexyl silane, trimethoxy cyclopentyloxy silane, trimethoxy cyclohexyloxy silane, ethyl dimethoxy cyclohexyl silane, methyl diethoxy cyclopentyl silane, methyl diethoxy cyclohexyloxy silane, methyl dimethoxy cyclopentyloxy silane, dimethyl ethoxy cyclohexyl silane, dimethyl methoxy cyclopentyl silane, dimethyl ethoxy cyclohexyloxy silane, dimethyl ethoxy cyclopentyloxy silane, cyclohexyl methyl dimethoxy silane and dicyclopentyl dimethoxy silane; the phosphorus-containing compound is at least one selected from tributyl phosphate, tricyclopentyl phosphate, dibutyl phosphite, 2-ethylhexyl phosphate, tributylphosphine, tricyclohexyl phosphine, tri-n-butyl phosphine and trihexyl phosphorus oxide; the sulfur-containing compound is at least one selected from dipentyl disulfide, 1, 9-nonyldithiol, n-dodecyl mercaptan, bis (16-hydroxyhexadecyl) disulfide and dicyclohexyl disulfide; the nitrogen-containing compound is at least one selected from the group consisting of tripentylamine, dihexylamine, dicyclohexylamine, spermine, spermidine, decylamine, 3-propylpiperidine, 4-piperidylpiperidine, (1-cyclopropylpyrrolidin-3-yl) methylamine, N, N, N ', N' -tetramethyl-1, 6-hexamethylenediamine, N-propylcyclohexylamine, N, N-dimethylcyclohexylamine.
The anti-adhesion agent is added into an olefin polymerization reaction system, so that the anti-adhesion agent contacts with a catalyst for olefin polymerization, the electronic effect and coordination space of an active site of the catalyst can be changed, the aim of reducing the content of low-molecular-weight polyolefin obtained by olefin polymerization is fulfilled, and the problems of adhesion of a polymerization system to a kettle and the like are further solved.
In one embodiment, the anti-sticking agent of the present invention is added during the preparation or formulation of the catalyst for olefin polymerization, i.e., the catalyst for olefin polymerization is prepared or formulated by adding the above-mentioned anti-sticking agent so that the anti-sticking agent contacts the catalyst. In another embodiment, the anti-sticking agent and the catalyst of the present invention are added during the olefin prepolymerization, i.e. the anti-sticking agent and the catalyst of the present invention are added simultaneously or sequentially during the olefin prepolymerization, so that the anti-sticking agent is contacted with the catalyst. In yet another embodiment, the antiblocking agent of the present invention and the catalyst may be mixed prior to adding the olefin polymerization system.
In one embodiment, the olefin polymerization process of the present invention comprises the steps of:
step 1, fully contacting a catalyst and an anti-adhesion agent;
step 2, mixing a cocatalyst with the mixture obtained in the step 1;
and 3, carrying out polymerization reaction on the olefin under the action of the mixture obtained in the step 2.
The catalyst of the present invention is not particularly limited as long as it can be used for olefin polymerization. For example, metallocene catalysts, constrained geometry metallocene catalysts (CGC), non-metallocene catalysts, supported constrained geometry metallocene catalysts (CGC) or supported non-metallocene catalysts. The anti-sticking agent can change the electronic effect and coordination space of active sites in the catalyst in the process of contacting with the catalyst, thereby achieving the purpose of reducing the content of low molecular weight polyolefin obtained by olefin polymerization.
In one embodiment, the catalyst of the present invention has a molar ratio of catalyst to antiblocking agent of 1:0.01-2, calculated as transition metal. The contact temperature of the catalyst and the anti-adhesion agent is-20-60 ℃, and stirring is carried out in the contact process, wherein the stirring time is 0.1-20 hours.
And then mixing the cocatalyst with the mixture obtained in the step 1, and further catalyzing olefin to carry out polymerization reaction.
The present invention is not particularly limited in the type of polymerization reaction, and is, for example, a solution polymerization process, a gas phase polymerization process, a liquid phase bulk polymerization process, a slurry polymerization process, a loop polymerization process, or a combination polymerization process. In addition, the olefin is not particularly limited in the present invention, and may be ethylene polymerization, propylene polymerization, copolymerization of ethylene with other carbon-carbon double bond-containing organic substances, copolymerization of propylene with other carbon-carbon double bond-containing organic substances, and further synthesis of polyolefin materials, flame-retardant polyolefin materials, and functionalized polyolefin materials. Wherein the other organic matter containing carbon-carbon double bond is selected from C 2 -C 30 Alpha-olefins, C 6 -C 30 Diene, C 3 -C 100 An oxygen-containing organic matter containing carbon-carbon double bonds; wherein said C 2 -C 30 The olefin of (C) is preferably selected from ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, dicyclopentadiene, norbornene or a mixture thereof, and the like; c (C) 3 -C 100 The oxygen-containing organic matter containing carbon-carbon double bonds is preferably selected from 7-octen-1-ol, 9-decen-1-ol or a mixture thereof, etc.
In one embodiment, the polymerization temperature is 20-200 ℃, the reaction time is 5-300min, and the gas pressure is 0.05-40MPa, so that the product is obtained; wherein the obtained product is high-end polyolefin material, such as mPE, POE, mPP, COC, COP, EPDM, EPR, POP, PMP, OBC.
In one embodiment, the olefin polymerization process of the present invention comprises the steps of:
(1) In a supported catalystAdding an organic solvent into a preparation tank of a homogeneous catalyst, a preparation tank of a supported catalyst or an olefin prepolymerization tank, adding a catalyst, adding an anti-sticking agent, and stirring for 0.1-20 hours at-20-60 ℃ to enable the active site of the catalyst to fully contact with anti-sticking agent molecules; wherein the catalyst may be a metallocene catalyst, constrained geometry metallocene catalyst (CGC), non-metallocene catalyst, supported constrained geometry metallocene catalyst (CGC), or supported non-metallocene catalyst; wherein the anti-adhesion agent can be any anti-adhesion agent; wherein the organic solvent is selected from C 5 -C 50 Saturated hydrocarbon of C 5 -C 50 Alicyclic hydrocarbon of (C) 6 -C 50 Aromatic hydrocarbon or C of (C) 3 -C 50 Preferably toluene, xylene, diphenyl ether, biphenyl, hexane, heptane, octane, decane, cyclohexane, petroleum ether, paraffin oil, white oil, dodecane, tetradecane or hexadecane, or a mixed solvent thereof; the mol ratio of transition metal to anti-adhesive in the catalyst is 1:0.01-2.
(2) Adding a cocatalyst into the mixture obtained in the step (1) at the temperature of-20-60 ℃, wherein the molar ratio of the transition metal to the cocatalyst in the catalyst is 1:10-1000, and stirring for 10-600min; wherein the cocatalyst is aluminum alkyl, aluminum alkoxide or a mixture thereof; further, the cocatalyst is selected from trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-t-butylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, MAO or modified MAO, etc., and can be used alone or in combination of several cocatalysts.
(3) Adding the catalyst prepared in the step (2) into a polymerization reactor, adding an organic solvent, catalyzing ethylene polymerization, propylene polymerization, copolymerization of ethylene and other carbon-carbon double bond-containing organic matters, and copolymerization of propylene and other carbon-carbon double bond-containing organic matters to synthesize a polyolefin material, a flame-retardant polyolefin material and a functional polyolefin material, wherein the other carbon-carbon double bond-containing organic matters are selected from C 2 -C 30 Alpha-olefins of (2)、C 6 -C 30 Diene, C 3 -C 100 An oxygen-containing organic matter containing carbon-carbon double bonds; wherein said C 2 -C 30 The olefin of (C) is preferably selected from ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, dicyclopentadiene, norbornene or a mixture thereof, and the like; c (C) 3 -C 100 The oxygen-containing organic matter containing carbon-carbon double bonds is preferably 7-octen-1-ol, 9-decen-1-ol or a mixture thereof; maintaining the polymerization temperature at 20-200 ℃, reacting for 5-300min, and obtaining a product, wherein the gas pressure is 0.05-40 MPa; wherein the polymerization process is a solution polymerization process, a gas phase polymerization process, a liquid phase bulk polymerization process, a slurry polymerization process, a loop polymerization process or a combination polymerization process; wherein the obtained product is a high-end polyolefin material, mPE, POE, mPP, COC, COP, EPDM, EPR, POP, PMP, OBC, etc.
In carrying out the olefin polymerization, the organic solvent used is selected from C 5 -C 50 Saturated hydrocarbon of C 5 -C 50 Alicyclic hydrocarbon of (C) 6 -C 50 Aromatic hydrocarbon or C of (C) 3 -C 50 Preferably toluene, xylene, diphenyl ether, biphenyl, hexane, heptane, octane, decane, cyclohexane, petroleum ether, paraffin oil, white oil, dodecane, tetradecane or hexadecane, or a mixed solvent thereof.
Therefore, in the preparation of mPE, POE, mPP, COC, COP, EPDM, EPR, POP, PMP, OBC and other reaction systems, the oxygen-containing compound, the nitrogen-containing compound, the sulfur-containing compound, the silicon-containing compound, the phosphorus-containing compound and other anti-sticking agents are added in the preparation or preparation process of the catalyst or in the olefin pre-polymerization process, so that the reaction system is not stuck to a kettle, a reactor, a stirrer, other accessories and pipes. Meanwhile, the invention relates to an olefin polymerization method of the anti-adhesive, which has the advantages of simplicity, low cost, low equipment requirement, low energy consumption and low environmental pollution.
The technical scheme of the invention will be further described in detail through specific examples. Wherein, the inclusion of the inclusion in parentheses such as "0.1wt% hexane solution" means that the addition of the solute is added in the form of a hexane solution having a solute concentration of 0.1 wt%. In addition, the anti-adhesion agent is generally a commercial product, and the synthesis of partial alkoxy silane compounds is disclosed in patent CN106317268A.
Example 1
(1) Drying a catalyst preparation tank, replacing with nitrogen, adding 20mL of normal hexane into the catalyst preparation tank at the temperature of minus 20 ℃, adding 30mg of dimethyl cyclopentadiene titanium trichloride, adding 0.12mL of anti-adhesion agent dimethyl methoxy cyclohexyl silane (0.1 wt% hexane solution), stirring for 6 minutes, adding 6mL of MAO (10 wt% toluene solution), and stirring for 600 minutes; (2) After a 2 liter stainless steel autoclave is fully replaced by nitrogen, 2mL of the catalyst prepared in the step (1) is measured at 20 ℃ and added into the 2 liter stainless steel autoclave, 0.1L of hydrogen is filled, ethylene is filled to the pressure of 0.05MPa, stirring is carried out, the reaction is carried out for 30 minutes, 11 g of polymerization product is collected, the kettle is not stuck, and the weight average molecular weight is 33 multiplied by 10 4 g/mol。
Example 2
(1) Drying the catalyst preparation tank, replacing with nitrogen, adding 10mL of n-hexane into the catalyst preparation tank at 30 ℃, adding 20mg of dimethyl silicon-based diindene titanium dichloride, adding 0.8mL of anti-adhesion agent methyl diethoxy cyclohexyloxy silane (1 wt% hexane solution), and stirring for 30 minutes; MAO 5mL (10 wt% toluene solution) was added and stirred for 30 minutes; (2) After a 2 liter stainless steel autoclave is fully replaced by nitrogen, 3mL of the catalyst prepared in the step (1) is measured at 25 ℃ and added into the 2 liter stainless steel autoclave, 0.2L of propylene is filled, ethylene is filled to the pressure of 0.9MPa, stirring and heating are carried out to 55 ℃ for 30 minutes, 122 g of polymerization product is collected, the kettle is not stuck, and the weight average molecular weight is 52 multiplied by 10 4 g/mol。
Example 3
(1) Drying the catalyst preparation tank, replacing with nitrogen, adding 30mL of n-hexane into the catalyst preparation tank at 60 ℃, and adding dimethyl silicon30mg of phenylanilino cyclopentadiene titanium dichloride was added to 2.4mL (1 wt% toluene solution) of methyl dimethoxy cyclohexyl silane as an anti-adhesive, and stirred for 40 minutes; MAO 40mL (10 wt% toluene solution) was added and stirred for 300 minutes; (2) After a 2 liter stainless steel autoclave is fully replaced by nitrogen, 2mL of the catalyst prepared in the step (1) is measured at 60 ℃ and added into the 2 liter stainless steel autoclave, 0.1L of propylene is filled, 30mL of 1-octene is filled, ethylene is filled to the pressure of 8MPa, stirring and heating is carried out to 160 ℃ for 5 minutes, 26 g of polymerization product is collected, and the polymerization product is not sticky, and the weight average molecular weight is 12 multiplied by 10 4 g/mol。
Example 4
(1) Drying a catalyst preparation tank, replacing with nitrogen, adding 30mL of n-hexane into the catalyst preparation tank at 30 ℃, adding 30mg of dimethylsilyl-2, 6-difluoroanilino cyclopentadiene titanium dichloride, adding 0.2mL of anti-adhesion agent dipentyl ether (1 wt% heptane solution), and stirring for 60 minutes; MAO8mL (10% toluene solution) was added and stirred for 60 minutes; (2) After a 2 liter stainless steel autoclave is fully replaced by nitrogen, 2mL of the catalyst prepared in the step (1) is measured at 30 ℃ and added into the 2 liter stainless steel autoclave, 30mL of 1-octene is filled, ethylene is filled to the pressure of 1.5MPa, stirring and heating is carried out to 145 ℃ for 20 minutes, 55 g of polymerization product is collected, the kettle is not stuck, and the weight average molecular weight is 115 multiplied by 10 4 g/mol。
Example 5
(1) Drying a catalyst preparation tank, replacing with nitrogen, adding 20mL of n-hexane into the catalyst preparation tank at 40 ℃, adding 30mg of silica supported dimethylsilyl anilino cyclopentadiene titanium dichloride (titanium content is 1.5 wt%) and adding 1.2mL of anti-sticking trimethoxy cyclohexyloxy silane (1 wt% hexane solution), and stirring for 300 minutes; 0.3mL of triethylaluminum (1.5M hexane solution) was added thereto and stirred for 300 minutes; (2) After a 2 liter stainless steel autoclave is fully replaced by nitrogen, 5mL of the catalyst prepared in the step (1) is measured at 40 ℃ and added into the 2 liter stainless steel autoclave, 10mL of 1-butene is filled, ethylene is filled to the pressure of 25MPa, stirring is carried out, the temperature is raised to 200 ℃ for reaction for 90 minutes, 131 g of polymerization product is collected, and the weight average molecular weight is 52 multiplied by 10 4 g/mol, and no adhesion to the kettle.
Example 6
(1) Will catalyzeDrying the preparation tank, replacing with nitrogen, adding 20mL of n-hexane into the preparation tank at the temperature of minus 20 ℃, adding 15mg of alpha-diimine nickel dibromide, adding 0.15mL of anti-adhesion agent cyclohexylmethyl dimethoxy silane (1 wt% hexane solution), and stirring for 30 minutes; MAO 7mL (10% toluene solution) was added and stirred for 30 minutes; (2) After a 2 liter stainless steel autoclave is fully replaced by nitrogen, 3mL of the catalyst prepared in the step (1) is measured at 30 ℃ and added into the 2 liter stainless steel autoclave, 10mL of styrene is filled, ethylene is filled to the pressure of 0.8MPa, stirring is carried out, the temperature is raised to 50 ℃ for 30 minutes, 35 g of polymerization product is collected, the kettle is not stuck, and the weight average molecular weight is 46 multiplied by 10 4 g/mol。
Example 7
(1) Drying the catalyst preparation tank, replacing with nitrogen, adding 20mL of n-hexane into the catalyst preparation tank at 30 ℃, adding 15mg of alpha-diimine nickel dibromide, adding 0.25mL of anti-adhesion agent tricyclopentyl phosphate (1 wt% hexane solution), and stirring for 30 minutes; MAO15mL (10% toluene solution) was added and stirred for 30 minutes; (2) After a 2 liter stainless steel autoclave is fully replaced by nitrogen, 3mL of the catalyst prepared in the step (1) is measured at 30 ℃ and added into the 2 liter stainless steel autoclave, 10mL of propylene is filled, ethylene is filled to the pressure of 0.8MPa, stirring is carried out, the temperature is raised to 50 ℃ for 30 minutes, 46 g of polymerization product is collected, the kettle is not adhered, and the weight average molecular weight is 49 multiplied by 10 4 g/mol。
Example 8
(1) Drying the catalyst preparation tank, replacing with nitrogen, adding 20mL of normal hexane into the catalyst preparation tank at 10 ℃, adding 15mg of alpha-diimine nickel dibromide, adding 1.3mL of anti-sticking agent tripentylamine (1 wt% hexane solution), and stirring for 20 hours; MAO15mL (10% toluene solution) was added and stirred for 600 minutes; (2) After a 2 liter stainless steel autoclave is fully replaced by nitrogen, 3mL of the catalyst prepared in the step (1) is measured at 30 ℃ and added into the 2 liter stainless steel autoclave, 10mL of propylene is filled, ethylene is filled to the pressure of 0.05MPa, stirring is carried out, the temperature of 10 ℃ is maintained for reaction for 300 minutes, 52 g of polymerization product is collected, the kettle is not stuck, and the weight average molecular weight is 44 multiplied by 10 4 g/mol。
Example 9
(1) Drying the catalyst preparation tank, replacing with nitrogen, and preparing the catalyst at 30deg.C20mL of n-hexane, 15mg of alpha-diimine nickel dibromide and 0.1mL of anti-adhesion agent dipentyl disulfide (1 wt% hexane solution) are added into a tank, and the mixture is stirred for 30 minutes; MAO15mL (10% toluene solution) was added and stirred for 30 minutes; (2) After a 2 liter stainless steel autoclave is fully replaced by nitrogen, 3mL of the catalyst prepared in the step (1) is measured at 30 ℃ and added into the 2 liter stainless steel autoclave, 10mL of propylene is filled, ethylene is filled to the pressure of 0.8MPa, stirring is carried out, the temperature is raised to 50 ℃ for 30 minutes, 41 g of polymerization product is collected, the kettle is not stuck, and the weight average molecular weight is 43 multiplied by 10 4 g/mol。
Example 10
(1) Drying a catalyst preparation tank, replacing with nitrogen, adding 20mL of normal hexane into the catalyst preparation tank at 60 ℃, adding 15mg of FI titanium catalyst, adding 0.1mL (1 wt% hexane solution) of anti-adhesion agent ethyl dimethoxy cyclohexyl silane, and stirring for 30 minutes; MAO15mL (10% toluene solution) was added and stirred for 30 minutes; (2) After a 2 liter stainless steel autoclave is fully replaced by nitrogen, 3mL of the catalyst prepared in the step (1) is measured at 30 ℃ and added into the 2 liter stainless steel autoclave, 10mL of propylene is filled, ethylene is filled to the pressure of 0.8MPa, stirring and heating to 80 ℃ are carried out for 30 minutes, 57 g of polymerization product is collected, the kettle is not adhered, and the weight average molecular weight is 45 multiplied by 10 4 g/mol。
Example 11
(1) Drying a catalyst preparation tank, replacing with nitrogen, adding 20mL of normal hexane into the catalyst preparation tank at 60 ℃, adding 15mg of FI titanium catalyst, adding 2mL (1 wt% hexane solution) of anti-adhesion agent ethyl dimethoxy cyclohexyl silane, and stirring for 10 hours; adding a toluene solution of MAO15 mLi% and stirring for 300 minutes; (2) After a 2 liter stainless steel autoclave is fully replaced by nitrogen, 3mL of the catalyst prepared in the step (1) is measured at 60 ℃ and added into the 2 liter stainless steel autoclave, 10mL of propylene is filled, ethylene is filled to the pressure of 40MPa, stirring and heating is carried out to 140 ℃ for 15 minutes, 94 g of polymerization product is collected, the kettle is not stuck, and the weight average molecular weight is 37 multiplied by 10 4 g/mol。
Example 12
(1) Drying the catalyst preparation tank, replacing with nitrogen, adding n-hexane 20mL into the catalyst preparation tank at 60deg.C, adding FI titanium catalyst 15mg, addingAnti-adhesion agent ethyl dimethoxy cyclohexyl silane 0.5mL (1 wt% hexane solution), stirring for 20 hours; MAO 7.5mL (10% toluene solution) was added and stirred for 600 minutes; (2) After a 2 liter stainless steel autoclave is fully replaced by nitrogen, 3mL of the catalyst prepared in the step (1) is measured at 60 ℃ and added into the 2 liter stainless steel autoclave, 10mL of propylene is filled, ethylene is filled to the pressure of 20MPa, stirring and heating to 200 ℃ are carried out for 5 minutes, 64 g of polymerization product is collected, the kettle is not stuck, and the weight average molecular weight is 31 multiplied by 10 4 g/mol。
Example 13
(1) Drying a catalyst preparation tank, replacing with nitrogen, adding 20mL of n-hexane into the catalyst preparation tank at 30 ℃, adding 30mg of silicon dioxide supported alpha-diimine titanium dichloride (titanium content is 1.1 wt%) and 0.1mL of anti-adhesion trimethoxy cyclohexyloxy silane (1 wt% hexane solution), and stirring for 30 minutes; MAO 5.5mL (10% toluene solution) was added and stirred for 30 min; (2) After a 2 liter stainless steel autoclave is fully replaced by nitrogen, 5mL of the catalyst prepared in the step (1) is measured at 30 ℃ and added into the 2 liter stainless steel autoclave, 10mL of 1-butene is filled, ethylene is filled to the pressure of 0.8MPa, stirring and heating to 65 ℃ are carried out for 90 minutes, 37 g of polymerization product is collected, and the weight average molecular weight is 51 multiplied by 10 4 g/mol, and no adhesion to the kettle.
Example 14
(1) Drying a catalyst preparation tank, replacing with nitrogen, adding 20mL of normal hexane into the catalyst preparation tank at 30 ℃, adding 20mg of anilino diphenyl phosphine titanium dichloride catalyst, adding 1mL of anti-adhesion dicyclopentyl dimethoxy silane (1 wt% hexane solution), and stirring for 30 minutes; MAO15mL (10% toluene solution) was added and stirred for 30 minutes; (2) Fully replacing a 2 liter stainless steel autoclave with nitrogen, adding the catalyst prepared in the step (1) into the 2 liter stainless steel autoclave at 30 ℃, filling 5mL of 9-decen-1-ol, heating to 50 ℃, filling ethylene to 0.8MPa, stirring and reacting for 30 minutes, collecting 15 g of polymerized product, and collecting the non-sticking autoclave with the weight average molecular weight of 50 multiplied by 10 4 g/mol。
Example 15
(1) The catalyst preparation tank is dried and replaced by nitrogen, 20mL of n-hexane is added into the catalyst preparation tank at 30 ℃,20mg of 2,4, 6-trimethylanilino diphenyl phosphine titanium dichloride catalyst is added, 0.1mL (0.1 wt% hexane solution) of anti-adhesion agent dicyclopentyl dimethoxy silane is added, and stirring is carried out for 20 hours; MAO15mL (10% toluene solution) was added and stirred for 100 minutes; (2) Fully replacing a 2 liter stainless steel autoclave with nitrogen, adding the catalyst prepared in the step (1) into the 2 liter stainless steel autoclave at 30 ℃, filling 5mL of 9-decen-1-ol, cooling to 0 ℃, filling ethylene to 0.05MPa, stirring for reaction for 30 minutes, collecting 5 g of polymerization product, and obtaining a non-sticking autoclave with a weight average molecular weight of 52 multiplied by 10 4 g/mol。
Example 16
(1) Drying a catalyst preparation tank, replacing nitrogen, adding 20mL of normal hexane into the catalyst preparation tank at 30 ℃, adding 20mg of 2, 6-difluoroanilino dicyclohexyl phosphine titanium dichloride catalyst, adding 15mL of MAO (10% toluene solution), adding 1mL of anti-adhesion dicyclopentyl dimethoxy silane (1 wt% hexane solution), and stirring for 30 minutes; (2) Fully replacing a 2 liter stainless steel autoclave with nitrogen, adding the catalyst prepared in the step (1) into the 2 liter stainless steel autoclave at 30 ℃, filling 5mL of 9-decen-1-ol, heating to 40 ℃, filling ethylene to the pressure of 0.8MPa, stirring and reacting for 30 minutes, collecting 15 g of a polymerization product, and collecting the catalyst without sticking to the autoclave, wherein the weight average molecular weight is 45 multiplied by 10 4 g/mol。
Example 17
(1) Drying a catalyst preparation tank, replacing nitrogen, adding 20mL of normal hexane into the catalyst preparation tank at 30 ℃, adding 20mg of 2,4, 6-trifluoroanilino dicyclohexylphosphine titanium dichloride catalyst, adding 30mL of MAO (10% toluene solution), stirring for 10 minutes, adding 0.1mL of anti-adhesive dicyclopentyl dimethoxy silane (1 wt% hexane solution), and stirring for 20 hours; (2) Fully replacing a 2 liter stainless steel autoclave with nitrogen, adding the catalyst prepared in the step (1) into the 2 liter stainless steel autoclave at 30 ℃, filling 5mL of 9-decen-1-ol, heating to 70 ℃, filling ethylene to the pressure of 0.3MPa, stirring and reacting for 5 minutes, collecting 8 g of a polymerization product, and collecting the catalyst without sticking to the autoclave, wherein the weight average molecular weight is 43 multiplied by 10 4 g/mol。
Example 18
(1) Catalyst is preparedDrying a preparation tank, replacing with nitrogen, adding 20mL of normal hexane into the catalyst preparation tank at 30 ℃, adding 20mg of 2, 6-difluoroanilino dicyclohexylphosphine titanium dichloride catalyst, adding 5mL of MAO (10% toluene solution), stirring for 600 minutes, adding 0.5mL of anti-adhesion dicyclopentyl dimethoxy silane (1 wt% hexane solution), and stirring for 10 hours; (2) Fully replacing a 2 liter stainless steel autoclave with nitrogen, adding the catalyst prepared in the step (1) into the 2 liter stainless steel autoclave at 30 ℃, filling 5mL of 9-decen-1-ol, cooling to-20 ℃, filling ethylene to the pressure of 12MPa, stirring for reacting for 300 minutes, collecting 38 g of polymerized product, and obtaining the catalyst with the weight average molecular weight of 83 multiplied by 10, wherein the catalyst is not sticky 4 g/mol。
Comparative example 1
(1) Drying the catalyst preparation tank, replacing with nitrogen, adding 20mL of n-hexane into the catalyst preparation tank at 30 ℃, adding 15mg of FI titanium catalyst, and stirring for 30 minutes; (2) After a 2 liter stainless steel autoclave was fully replaced with nitrogen, 3mL of the prepared catalyst was measured at 30℃and added to the 2 liter stainless steel autoclave, 15mL of MAO (10% toluene solution) was added, 10mL of propylene was charged, ethylene was charged to a pressure of 0.8MPa, stirring was conducted, the temperature was raised to 50℃for 30 minutes, 5 g of a polymerization product was collected, and the mixture was stirred to obtain a reactor having a weight average molecular weight of 7.5X10 4 g/mol。
Comparative example 2
(1) Drying the catalyst preparation tank, replacing with nitrogen, adding 20mL of n-hexane into the catalyst preparation tank at 30 ℃, adding 15mg of alpha-diimine nickel dibromide, and stirring for 30 minutes; (2) After a 2 liter stainless steel autoclave was fully replaced with nitrogen, 3mL of the prepared catalyst was measured at 30℃and added to the 2 liter stainless steel autoclave, 15mL of MAO (10% toluene solution) was added, 10mL of propylene was charged, ethylene was charged to a pressure of 0.8MPa, stirring was conducted, the temperature was raised to 50℃for 30 minutes, 4 g of a polymerization product was collected, and the mixture was stirred to give a reactor having a weight average molecular weight of 6.5X10 4 g/mol。
Comparative example 3
(1) Drying the catalyst preparation tank, replacing with nitrogen, adding 30mL of n-hexane into the catalyst preparation tank at 30 ℃, adding 30mg of dimethylsilyl-2, 6-difluoroanilino cyclopentadiene titanium dichloride, and stirring for 60 minutes; (2) 2 liter stainless steel autoclaveAfter being fully replaced by nitrogen, 2mL of the prepared catalyst is measured at 30 ℃ and added into a 2 liter stainless steel autoclave, 8mL of MAO (10% toluene solution) is added, 30mL of 1-octene is filled, ethylene is filled to the pressure of 0.8MPa, stirring and heating to 55 ℃ are carried out for 20 minutes, 2 g of polymerization product is collected, and the polymerization product is adhered to the autoclave, and the weight average molecular weight is 55 multiplied by 10 4 g/mol。
Comparative example 4
(1) Drying the catalyst preparation tank, replacing with nitrogen, adding 20mL of n-hexane into the catalyst preparation tank at 20 ℃, adding 30mg of dimethyl cyclopentadiene titanium trichloride, and stirring for 20 minutes; (2) After the 2L stainless steel autoclave is fully replaced by nitrogen, 2mL of the prepared catalyst is measured at 20 ℃ and added into the 2L stainless steel autoclave, 6mL of MAO (10% toluene solution) is added, 0.1L of hydrogen is filled, ethylene is filled to the pressure of 0.7MPa, stirring and heating to 55 ℃ for reaction for 1 hour, 2 g of polymerization product is collected, and the mixture is adhered to a kettle, wherein the weight average molecular weight of the mixture is 3.5 multiplied by 10 4 g/mol。
Comparative example 5
(1) Drying the catalyst preparation tank, replacing with nitrogen, adding 30mL of n-hexane into the catalyst preparation tank at 30 ℃, adding 30mg of dimethylsilyl anilino cyclopentadiene titanium dichloride, and stirring for 40 minutes; (2) After a 2 liter stainless steel autoclave was fully replaced with nitrogen, 2mL of the prepared catalyst was measured at 30℃and added to the 2 liter stainless steel autoclave, MAO8mL (10% toluene solution) was added, 0.1L of propylene was charged, 30mL of 1-octene was charged, 0.7mL of anti-sticking methyldimethoxycyclohexylsilane was added, ethylene was charged to a pressure of 0.8MPa, stirred, heated to 65℃and reacted for 30 minutes, 4.5 g of a polymerization product was collected, and the weight average molecular weight was 25X 10 in a viscous autoclave 4 g/mol。
Comparative example 6
(1) Drying the catalyst preparation tank, replacing with nitrogen, adding 20mL of n-hexane into the catalyst preparation tank at 30 ℃, adding 20mg of 2, 6-difluoroanilino dicyclohexylphosphine titanium dichloride catalyst, adding 15mL of MAO (10% toluene solution), and stirring for 30 minutes; (2) After the 2L stainless steel autoclave is fully replaced by nitrogen, the prepared catalyst is fully added into the 2L stainless steel autoclave at 30 ℃, 5mL of 9-decen-1-ol is filled, the temperature is raised to 40 ℃, and ethylene is filled until the pressure is the same0.8MPa, stirring and reacting for 30 minutes, collecting 12 g of polymerization product, sticking to a kettle, and having a weight average molecular weight of 15 multiplied by 10 4 g/mol。
As can be seen from the above examples and comparative examples, the addition of the anti-sticking agent of the present invention can improve the pot adhesion during polymerization. The term "adhesive pot" in the present invention means that the polymer is adhered in the form of filament and powder agglomerate in the equipment. In general, when polymerization is carried out in smaller equipment, whether a kettle is stuck or not can be directly observed and judged in the reaction process or after the reaction is finished; when the polymerization is carried out in large equipment, whether the kettle is stuck or not can be judged indirectly through parameters such as the load of power equipment, and whether the kettle is stuck or not can be judged by directly observing after the polymerization is finished.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (12)

1. An anti-sticking agent for an olefin polymerization reaction system, characterized in that the anti-sticking agent comprises at least one of an oxygen-containing compound, a nitrogen-containing compound, a sulfur-containing compound, a silicon-containing compound and a phosphorus-containing compound, wherein the oxygen-containing compound has a general formula I, the nitrogen-containing compound has a general formula II, the sulfur-containing compound has a general formula III, the silicon-containing compound has a general formula IV, the phosphorus-containing compound has a general formula V or VI,
wherein, -R 1 、-R 2 Is hydrocarbon, and the total carbon number is between 8 and 60;
-R 3 、-R 4 、-R 5 is-H or alkyl, and the total carbon number is between 8 and 60;
-R 6 、-R 7 is-H or alkyl, and the total carbon number is between 8 and 60;
-R 8 、-R 9 、-R 10 、-R 11 is hydrocarbon or hydrocarbyloxy, the total carbon number is between 8 and 60;
-R 12 、-R 13 、-R 14 is-H, alkyl or alkoxy, and the total carbon number is 8-60.
2. An anti-sticking agent for an olefin polymerization system according to claim 1, wherein R 1 and-R 2 A total carbon number of between 8 and 30, -R 3 、-R 4 、-R 5 A total carbon number of between 8 and 30, -R 6 、-R 7 A total carbon number of between 8 and 30, -R 8 、-R 9 、-R 10 、-R 11 A total carbon number of between 8 and 30, -R 12 、-R 13 、-R 14 And the total carbon number of (2) is between 8 and 30.
3. The anti-sticking agent for olefin polymerization system according to claim 2, wherein the oxygen-containing compound is at least one selected from dibutyl ether, dipentyl ether, dihexyl ether, diheptyl ether and diphenyl ether; the silicon-containing compound is at least one selected from methyl dimethoxy cyclohexyl silane, methyl dimethoxy cyclopentyl silane, trimethoxy cyclohexyl silane, trimethoxy cyclopentyloxy silane, trimethoxy cyclohexyloxy silane, ethyl dimethoxy cyclohexyl silane, methyl diethoxy cyclopentyl silane, methyl diethoxy cyclohexyloxy silane, methyl dimethoxy cyclopentyloxy silane, dimethyl ethoxy cyclohexyl silane, dimethyl methoxy cyclopentyl silane, dimethyl ethoxy cyclohexyloxy silane, dimethyl ethoxy cyclopentyloxy silane, cyclohexyl methyl dimethoxy silane and dicyclopentyl dimethoxy silane; the phosphorus-containing compound is at least one selected from tributyl phosphate, tricyclopentyl phosphate, dibutyl phosphite, 2-ethylhexyl phosphate, tributylphosphine, tricyclohexyl phosphine, tri-n-butyl phosphine and trihexyl phosphorus oxide; the sulfur-containing compound is at least one selected from dipentyl disulfide, 1, 9-nonyldithiol, n-dodecyl mercaptan, bis (16-hydroxyhexadecyl) disulfide and dicyclohexyl disulfide; the nitrogen-containing compound is at least one selected from the group consisting of tripentylamine, dihexylamine, dicyclohexylamine, spermine, spermidine, decylamine, 3-propylpiperidine, 4-piperidylpiperidine, (1-cyclopropylpyrrolidin-3-yl) methylamine, N, N, N ', N' -tetramethyl-1, 6-hexamethylenediamine, N-propylcyclohexylamine, N, N-dimethylcyclohexylamine.
4. An olefin polymerization system, wherein the anti-sticking agent according to any one of claims 1 to 3 is added to the olefin polymerization system.
5. An olefin polymerization process wherein an olefin is used as a raw material and the polymerization is carried out under the action of a catalyst and the anti-sticking agent according to any one of claims 1 to 3.
6. The method for polymerizing olefins according to claim 5, wherein the anti-sticking agent is added during the preparation or the preparation of the catalyst, or the anti-sticking agent and the catalyst are added during the prepolymerization of olefins.
7. The method of olefin polymerization of claim 5 wherein the catalyst is a metallocene catalyst, a constrained geometry metallocene catalyst, a non-metallocene catalyst, a supported constrained geometry metallocene catalyst, or a supported non-metallocene catalyst.
8. The method for polymerizing olefins according to claim 5, wherein the polymerization is a solution polymerization, a gas phase polymerization, a liquid phase bulk polymerization, a slurry polymerization, a loop polymerization or a combination polymerization.
9. The olefin polymerization process of claim 5, comprising the steps of:
step 1, fully contacting the catalyst and the anti-adhesion agent;
step 2, mixing a cocatalyst with the mixture obtained in the step 1;
and 3, carrying out polymerization reaction on the olefin under the action of the mixture obtained in the step 2.
10. The process for the polymerization of olefins according to claim 9 wherein the molar ratio of catalyst to anti-sticking agent is 1:0.01-2 and the molar ratio of catalyst to co-catalyst is 1:10-1000, calculated as transition metal; the cocatalyst is at least one selected from trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-tert-butylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methoxyaluminum and modified methoxyaluminum.
11. The method for polymerizing olefins according to claim 9, wherein the polymerization of olefins is ethylene polymerization, propylene polymerization, copolymerization of ethylene with other organic matters having carbon-carbon double bond, copolymerization of propylene with other organic matters having carbon-carbon double bond, wherein the other organic matters having carbon-carbon double bond are selected from C 2 -C 30 Alpha-olefins, C 6 -C 30 Diene, C 3 -C 100 An oxygen-containing organic compound containing a carbon-carbon double bond, said C 2 -C 30 The alpha-olefin of (C) is preferably selected from ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, dicyclopentadiene, norbornene or mixtures thereof 3 -C 100 Preferably, the oxygen-containing organic matter containing carbon-carbon double bonds is selected from 7-octen-1-ol, 9-decen-1-ol or a mixture thereof.
12. The process for polymerizing olefins according to claim 9, wherein the polymerization is carried out at a temperature of 20 to 200℃for a period of 5 to 300 minutes and a gas pressure of 0.05 to 40MPa.
CN202210971764.XA 2022-08-12 2022-08-12 Olefin polymerization system, method and anti-sticking agent used in same Pending CN117624415A (en)

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