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CN111087499B - Ziegler-Natta catalyst system and use thereof and polyolefin and olefin polymerization - Google Patents

Ziegler-Natta catalyst system and use thereof and polyolefin and olefin polymerization Download PDF

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CN111087499B
CN111087499B CN201811239717.6A CN201811239717A CN111087499B CN 111087499 B CN111087499 B CN 111087499B CN 201811239717 A CN201811239717 A CN 201811239717A CN 111087499 B CN111087499 B CN 111087499B
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antioxidant
olefin polymerization
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宋文波
毕福勇
陈明
李德展
陈江波
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
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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
    • 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
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    • C08K5/00—Use of organic ingredients
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    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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    • C08K5/00—Use of organic ingredients
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Abstract

The invention relates to the field of polymers, and particularly discloses a Ziegler-Natta catalyst system and application thereof, and polyolefin and olefin polymerization reaction. The olefin polymerization reaction comprises the step of carrying out olefin polymerization reaction on olefin in the presence of a Ziegler-Natta catalyst system containing a component A, a component B and a component C, wherein the component A is a magnesium chloride supported Ziegler-Natta catalyst containing Ti and an internal electron donor, the component B is a mixture of organic aluminum and an antioxidant with the molar ratio of 1 (1-100), and the component C is an external electron donor. The olefin polymerization reaction provided by the invention needs less antioxidant amount, the antioxidant is more uniformly dispersed in the polymer than that added in the subsequent processing stage, more excellent antioxidant effect can be achieved by using less antioxidant, the effect of improving the thermal stability of the polyolefin is remarkable, and the processing flow is simplified.

Description

Ziegler-Natta catalyst system and use thereof and polyolefin and olefin polymerization
Technical Field
The invention belongs to the field of polymers, and particularly relates to a Ziegler-Natta catalyst system and application thereof, and polyolefin and olefin polymerization reaction.
Background
It is known that polymers are oxidized by oxygen in the air to generate free radicals and peroxy radicals under the action of light, heat or physical stimuli during thermal processing and long-term use, so that the polymer material is deteriorated, mechanical properties thereof are lost, and the appearance is damaged. The antioxidant can effectively capture free radicals to prevent oxidation and decompose unstable hydroperoxide into stable compounds, thereby effectively reducing the autoxidation reaction of plastic materials, delaying the aging degradation of polymers and improving the thermal stability of the polymers.
In order to improve the thermal stability of the polymer product, an antioxidant is added by means of blending and the like in the processing process, so that the polymer product can be used for a long time. The hindered phenol antioxidant is widely applied, so that the performance reduction of the polymer in the using process is delayed, and the service cycle is prolonged. The hindered phenolic antioxidants commonly used are mainly: pentaerythrityl tetrakis [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), octadecanol beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (antioxidant 1330).
CN107674361A adopts phenol main antioxidant and two special auxiliary antioxidants to compound, and mechanically blends the compound with polyolefin products to obtain the stabilized polyolefin resin material.
CN105482250B, CN104419015B and CN103450379B adopt a composition formed by hindered phenol, phosphite ester, stearate, sodium borohydride and the like to blend with polyolefin products, which can effectively improve the thermal stability of the polymer, prevent the color change of the polymer by eliminating chromophoric groups, reduce the yellow index and improve the beauty and durability of the products, but the preparation method is in the product processing process.
CN103819596B discloses a high isotactic poly-1-butene and a preparation method thereof by in-kettle synthesis. The method adopts an in-kettle synthesis method of adding the nucleating agent in the polymerization stage, can obviously improve the crystallinity of the poly-1-butene, shorten the crystal form transformation time and improve the mechanical property.
At present, the preparation method for adding the antioxidant in the polymerization stage to improve the oxidation resistance of the polymer has not been reported, and particularly, the preparation method is not mentioned in the preparation process of the 1-butene polymer.
Disclosure of Invention
The object of the present invention is to provide a new Ziegler-Natta catalyst system and its use and for the polymerization of polyolefins and olefins.
After intensive research, the inventor of the invention finds that when organic aluminum and an antioxidant are added in a polymerization reaction stage and the molar ratio of the organic aluminum to the antioxidant is controlled to be 1 (1-100), the organic aluminum and the antioxidant can form a stable and uniform antioxidant shielding body structure, the antioxidant shielding body structure can be matched with a magnesium chloride supported Ziegler-Natta catalyst containing Ti and an internal electron donor in a Ziegler-Natta catalyst system and the external electron donor to initiate olefin polymerization, and the oxidation resistance of polyolefin can be improved, so that the purpose of preparing polyolefin with excellent thermal stability is achieved. Based on this, the present invention has been completed.
The invention specifically provides a Ziegler-Natta catalyst system, which comprises a component A, a component B and a component C, wherein the component A is a magnesium chloride supported Ziegler-Natta catalyst which contains Ti and an internal electron donor, the component B is a mixture of organic aluminum and an antioxidant, the molar ratio of the organic aluminum to the antioxidant is 1 (1-100), and the component C is an external electron donor.
The invention also provides the use of the above Ziegler-Natta catalyst system in olefin polymerization.
The present invention also provides an olefin polymerisation reaction wherein the olefin polymerisation reaction comprises subjecting an olefin to an olefin polymerisation reaction in the presence of the above Ziegler-Natta catalyst system.
In addition, the invention also provides the polyolefin prepared by the method.
The method for preparing the polyolefin has the advantages that the required antioxidant amount is less, the antioxidant is more uniformly dispersed in the polymer than that added in the subsequent processing stage, the more excellent antioxidant effect can be achieved by using less antioxidant amount, the effect of improving the thermal stability of the polyolefin is obvious, the method is particularly suitable for improving the thermal stability of the 1-butene polymer, is particularly suitable for an intermittent small-body polymerization device, simplifies the processing flow of the polymer, has great advantages in long-term storage of powder and post-processing of the polymer with high melt index and high viscosity, and can greatly reduce the processing difficulty and cost.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
The Ziegler-Natta catalyst system provided by the invention comprises a component A, a component B and a component C, wherein the component A is a magnesium chloride supported Ziegler-Natta catalyst which contains Ti and an internal electron donor, the component B is a mixture of organic aluminum and an antioxidant, the molar ratio of the organic aluminum to the antioxidant is 1 (1-100), and the component C is an external electron donor. Wherein, when the molar ratio of the organic aluminum to the antioxidant is out of the range of 1 (1-100), the content of the antioxidant is low, and the antioxidant effect is not obvious; or the content of the antioxidant is too high, so that flocculent precipitates are easily formed, the dispersing effect of the antioxidant is poor, and the precipitates are easily generated in the pump in the conveying process.
The organic aluminum and the antioxidant can react to form a stable and uniform compound in the polymerization reaction process, so that the compound has the cocatalyst function of the organic aluminum and the antioxidant function of the antioxidant, the dispersing effect of the antioxidant is good, the phase splitting problem existing in the blending of the antioxidant and the polymer in the processing process can be effectively avoided, the dosage of the required antioxidant is less than that of the antioxidant blended in the subsequent processing process, and the effect is better.
The antioxidant may be any one of various antioxidants suitable for improving the antioxidant property of polyolefin, for example, the antioxidant may be at least one selected from phenolic antioxidants, phosphite antioxidants, amine antioxidants and thioester antioxidants, preferably phenolic antioxidants, and the phenolic antioxidants may be at least one selected from monophenol, bisphenol, thiobisphenol and polyphenol.
The phenolic antioxidant is preferably a hindered phenolic antioxidant having a structure represented by formula (1):
Figure BDA0001838987610000041
wherein R is 1 And R 2 Each independently is a hydrogen atom, C 1 -C 5 Alkyl of (C) 5 -C 7 Cycloalkyl or C 7 -C 9 Is R is absent or is C 1 -C 8 N is an integer of 1 to 4, when n is 1, T represents C 1 -C 5 Alkyl of (C) 5 -C 7 Cycloalkyl or C 7 -C 9 When n is 2-4, T represents a direct bond, C 1 -C 30 Is an optionally heteroatom-substituted n-valent hydrogenated hydrocarbon radical, ca, mg or S, X being a flexible structural unit, a benzene or heteroaromatic ring having a rigid structure or a structural unit which is both flexible and rigid.
According to the present invention, it is particularly preferable that X has any one of the structures represented by the following formulae (1-1) to (1-11):
Figure BDA0001838987610000042
Figure BDA0001838987610000051
when n is 1, R 3 -R 5 Each independently H, C 1 -C 18 Or a heterocyclic ring bonded to T; when n is 2-4When R is 3 -R 5 Each independently H, C 1 -C 18 Alkyl of (a), a heterocyclic ring bonded to T or with another R 3 A heterocycle formed by the combination; r 6 Is absent or is C 1 -C 5 An alkylene group of (a); r is 7 -R 9 Each independently is H or C 1 -C 5 Alkyl group of (1).
The hindered phenol antioxidant may be specifically selected from at least one of the compounds represented by the following formulae (2-1) to (2-18):
Figure BDA0001838987610000052
Figure BDA0001838987610000061
Figure BDA0001838987610000071
Figure BDA0001838987610000081
Figure BDA0001838987610000091
the Ziegler-Natta catalyst system is a stereospecific catalyst. Wherein the molar ratio of the component A to the component B is preferably 1 (10-500), more preferably 1 (25-100) in terms of titanium/aluminum. The molar ratio of component C to component B, calculated as aluminum, is preferably (0.005-0.5): 1, more preferably (0.01-0.4): 1.
The Ziegler-Natta solid catalyst active component of component a is well known to those skilled in the art and can be prepared by methods well known in the art, for example, as disclosed in the following patent documents: CN85100997A, CN98126383.6, CN98111780.5, CN98126385.2, CN93102795.0, CN00109216.2, CN99125566.6, CN99125567.4, CN02100900.7, CN102453162, CN103819586, CN104610474, CN104610475, CN104610476, CN104610477, CN104610478, CN105622800, CN106543314, CN106543313, CN106543312, CN106543310, CN106554439, CN107522800, CN107522803.
The internal electron donor in the component A can be at least one selected from carboxylic ester compounds, ether compounds, 1,3-alcohol ester compounds and sulfonamide compounds, preferably at least one selected from phthalic ester compounds, 1,3-diether compounds, glycol ester compounds and succinate ester compounds, and most preferably 1,3-diether compounds.
The organoaluminum is preferably provided with AlR n X (3-n) An alkylaluminum compound of the structure and/or an alkylaluminoxane, R is C 1 -C 20 Alkyl radical, C 7 -C 20 Aralkyl or C 6 -C 20 Aryl, X is halogen, and n is an integer of 0 to 3. Wherein the compound has AlR n X (3-n) The alkylaluminum compound of structure (la) is preferably at least one selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-butylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, dimethylaluminum monochloride, diisobutylaluminum monochloride, isobutylaluminum dichloride, tris (2-methyl-3-phenyl-butyl) aluminum and tris (2-phenyl-butyl) aluminum. The alkylaluminoxane is preferably at least one selected from the group consisting of methylaluminoxane, tetra (isobutyl) aluminoxane, tetra (2,4,4-trimethyl-pentyl) aluminoxane, tetra (2,3-dimethylbutyl) aluminoxane and tetra (2,3,3-trimethylbutyl) aluminoxane.
The external electron donor may be at least one selected from the group consisting of a siloxane compound, an aminosilane compound, an organic amine compound, and an ether compound. Among them, the siloxane-based compound is preferably at least one selected from the group consisting of trimethylmethoxysilane, trimethylethoxysilane, methyl-t-butyldimethoxysilane, cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, dicyclopentyldimethoxysilane, isobutylcyclohexyldimethoxysilane, tetraethoxysilane and n-propenotriethoxysilane. The aminosilane compound is preferably at least one selected from the group consisting of diethylaminotriethoxysilane, 3-aminopropyltriethoxysilane, diethylaminomethyltriethoxysilane, dimethylaminomethyltriethoxysilane, diisopropylaminomethyltriethoxysilane, di-n-propylaminomethyltriethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, piperidinyltriethoxysilane and pyrrolyltriethoxysilane. The organic amine compound is preferably selected from the group consisting of aziridine, azetidine, pyrrolidine, azepane, azocane, -dimethyl aziridine, -tetramethyl azetidine, -tetraethylazetidine, -tetramethyl azetidine, -tetramethyl pyrrolidine, -tetraethylpyrrolidine, -tetra-n-propyl pyrrolidine, -tetraisopropyl pyrrolidine, -tetraisobutyl pyrrolidine, -tetramethyl piperidine, -tetraethylpiperidine, -tetra-n-propyl piperidine, -tetraisopropyl piperidine, and-tetraisobutylpiperidine, -tetramethylpiperidine, -tetraethylpiperidine, 2-methyl-2-cyclohexyl-6-methyl-6-ethylpiperidine, -dicyclopentyl-dimethylpiperidine, -tetramethylazepane, -tetraethylazepane, -tetra-n-propylazepane, -tetraisopropylazepane, -tetraisobutylazepane, -tetramethylazepane, -tetraethylazepane, -tetramethylazepane, -tetraethylazepane, -2-methyl-2-cyclohexyl-7-methyl-7-azepane, -dicyclopentyl-dimethylazepane, 2,2,8,8-tetramethylazocane, 2,2,8,8-tetraethylazocane, 2,2,8,8-tetra-n-propylazocane, 2,2,8,8-tetraisopropyl azocane, 2,2,8,8-tetra-n-butyl azocane, 2,2,8,8-tetraisobutyl azocane, 2,2,7,7-tetramethylazocane, 2,2,6,6-tetramethylazocane, 3,3,5,5-tetramethylazocane, and 3,3,6,6-tetramethylazocane. The ether compound is preferably at least one selected from the group consisting of compounds of the following general formula:
Figure BDA0001838987610000111
wherein R is 1 And R 2 Each independently selected from C 1 -C 20 One of linear, branched or cyclic aliphatic radicals, R 3 、R 4 、R 5 、R 6 、R 7 And R 8 Each independently selected from a hydrogen atom, a halogen atom, C 1 -C 20 Straight or branched alkyl of (2), C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl radical, C 7 -C 20 Alkylaryl and C 7 -C 20 One of aralkyl radicals, and R 3 、R 4 、R 5 、R 6 、R 7 And R 8 Optionally linked to form a ring. Specific examples of the ether compound include, but are not limited to: 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-phenyl-1,3-dimethoxypropane, 2,2-benzyl-1,3-dimethoxypropane, 2-isopropyl-2-isoamyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-isopropyl-2-3,7-dimethyloctyl-dimethoxypropane, 2,2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,2-diisobutyl-57 zxft 3757-diethoxypropane, 5852 zxft 355852-diisobutyl-3575-zxft 3575-dipropoxypropane, dipropyl-2 zxft-3825-dimethoxypropane, and at least one of the group consisting of dipropyloxy-2-propyl-3428 zxft-isopropyl-3428-isopropyloxy-2-isopentyl-3825-3625-isopropyloxy-3428-dimethoxypropane.
The invention also provides the use of said Ziegler-Natta catalyst system in the polymerization of olefins.
The present invention also provides an olefin polymerisation reaction wherein the olefin polymerisation reaction comprises subjecting an olefin to an olefin polymerisation reaction in the presence of the above Ziegler-Natta catalyst system.
The kind of the olefin is not particularly limited in the present invention, and may be 1-butene or a mixture of 1-butene and an α -olefin. When the olefin is a mixture of 1-butene and an alpha-olefin, it is particularly preferred that the 1-butene is used in an amount of 70 to 99.9mol% and the alpha-olefin is used in an amount of 0.1 to 30mol%. Among them, the α -olefin is a monoolefin having a double bond of 2 to 20 carbon atoms at the molecular chain terminal other than 1-butene, and particularly preferably at least one selected from the group consisting of 1-hexene, 1-octene and 1-decene.
The concentration of the organoaluminum in the system is preferably 0.1 to 10mol/L, more preferably 0.5 to 5mol/L. Can be prepared by diluting with an inert solvent. The inert solvent is at least one of n-hexane, heptane, n-octane and isohexane, preferably n-hexane. At the above concentration, the organoaluminum compound and the antioxidant can form a shielding structure more efficiently, and the reaction between the two is not so severe. Furthermore, the Ziegler-Natta catalyst system is preferably used in such an amount that the antioxidant component of the resulting polyolefin is present in an amount of 40ppm or more, preferably 40 to 2000ppm.
In the present invention, the conditions for the olefin polymerization reaction are not particularly limited, and it is preferable that the melt index of the obtained polyolefin at 190 ℃ under 2.16kg is 0.1 to 1000g/10min. Typically including a temperature of from 20 to 100 deg.C, more preferably from 30 to 80 deg.C, and most preferably from 50 to 80 deg.C; the time is 0.5-3h, more preferably 0.8-2.5h, most preferably 1-2h. Furthermore, the olefin polymerization can be carried out as a continuous or batchwise polymerization, it also being possible to carry out the polymerization process in the gas phase, in particular in one or more fluidized or mechanically stirred bed reactors.
According to the invention, in the olefin polymerization reaction process, a chain transfer agent is usually adopted to regulate and control the molecular weight of the polymer, namely hydrogen with different proportions is added into a reaction system as a molecular weight regulator; the molecular weight can also be controlled by controlling the reaction temperature. When hydrogen is used as the molecular weight regulator, the partial pressure of hydrogen may be 0.1 to 2.5MPa. In the present invention, the pressures are gauge pressures.
In addition, a known prepolymerization step may be added prior to the olefin polymerization. The prepolymerization is to add the catalyst into a small amount of monomer for reaction at low temperature, so as to ensure that the catalyst can keep good activity and form in the subsequent polymerization. The prepolymerization can be carried out continuously in bulk or batchwise in the presence of an inert solvent, and the prepolymerization temperature can be from 5 to 30 ℃. A precontacting step may optionally be provided before the prepolymerization step. The pre-contact refers to the pre-complexing process of the solid active component of the catalyst in the presence of organic aluminum and an external electron donor, so that the solid active component of the catalyst is converted into a catalyst system with polymerization activity, and the pre-contact temperature is generally 5-30 ℃.
According to one embodiment of the present invention, the olefin polymerization reaction comprises:
s1, heating a polymerization reaction kettle (the temperature can be 60-85 ℃) and purging with nitrogen to remove air and trace water in the polymerization reaction kettle;
s2, introducing hydrogen and the Ziegler-Natta catalyst system into the polymerization reaction kettle;
s3, adding the olefin into a polymerization reaction kettle, controlling the stirring speed to be 400-600rpm/min, reacting for 0.5-3h at 20-100 ℃, and stopping the reaction;
and S4, discharging the obtained polymer into a device with hot water, leaching the polymer with a hydroxyl-containing compound (such as water, alcohol and the like) after the unreacted olefin monomer is basically volatilized (more than 90 percent), and drying.
The polyolefin prepared by the method provided by the invention can realize in-situ polymerization of the antioxidant, has better dispersibility in the polymer, reduces the using amount of the antioxidant, can effectively improve the antioxidant performance of the polymer, effectively reduces the post processing cost of a high-viscosity system, is suitable for continuous polymerization and intermittent polymerization, is particularly suitable for intermittent small-body polymerization, and can effectively solve the problem of long-time storage degradation of powder and high-index polymer. When the content of the antioxidant is ensured to be more than 40ppm, preferably 40-2000ppm, the oxidation resistance of the polymer is obviously improved.
In addition, the invention also provides the polyolefin prepared by the method.
The polyolefin preferably has a molar content of alpha-olefin derived units of from 0.1 to 30% based on the total molar amount of olefin derived units, the polyolefin preferably has an antioxidant content of 40ppm or more, more preferably from 40 to 2000ppm, and the polyolefin preferably has a melt index of from 0.1 to 1000g/10min at 190 ℃ under 2.16 kg.
The present invention is further illustrated by the following examples. It is to be understood, however, that these examples are for the purpose of illustration and explanation only and are not intended to limit the present invention.
In the following examples and comparative examples, mgCl 2 /TiCl 4 The supported Ziegler-Natta catalyst is prepared by the following method: 200mL of white oil, 8.0g (0.08 mol) of magnesium chloride, 3g (0.01 mol) of octadecanol, 95mL (1.6 mol) of ethanol and 9.8mL (0.08 mol) of 2,2-dimethoxypropane are put into a 1.6L reaction kettle, and the temperature is raised to 90 ℃ under stirring; after reacting at constant temperature for 1 hour, dispersing the mixture for 30 minutes by stirring at low speed (stirring speed is 400 rpm) to emulsify; adding 35mL (0.45 mol) of epoxy chloropropane into the emulsified product, reacting for half an hour, and performing filter pressing for 9 minutes; washing the filter-pressing product with hexane for 5 times, and filter-pressing after washing each time, wherein the total time of the filter-pressing process is 20 minutes. Finally, vacuum drying the product to obtain a magnesium-containing carrier Z1; adding 100mL of titanium tetrachloride into a 300mL glass reaction bottle, cooling to-20 ℃, adding 8 g of the magnesium-containing carrier Z1, stirring at-20 ℃ for 30min, then slowly raising the temperature to 110 ℃, adding 1.5mL of diisobutyl phthalate in the process of raising the temperature, filtering the liquid after maintaining at 110 ℃ for 30min, then adding titanium tetrachloride and washing for 2 times to obtain a solid product, adding 100mL of titanium tetrachloride into the solid product, reacting at 25 ℃ for 16 h, finally washing for 4 times with hexane, and drying to obtain MgCl 2 /TiCl 4 A supported Ziegler-Natta catalyst.
In the following examples and comparative examples, the polymer-related data were obtained according to the following test methods:
(1) Melting Point (T) m ) The determination of (1): determined by Differential Scanning Calorimetry (DSC) in a Perkin Elmer DSC-7. 5 + -1 mg of sample are weighed and added at a rate of 10 deg.C/min in a nitrogen streamHeat to 180 ℃ and hold at 180 ℃ for 5min to completely melt all crystallites. Then cooled to-20 ℃ at a rate of 10 ℃/min, and the peak temperature is taken as the crystallization temperature. Standing at-20 deg.C for 5min, heating to 180 deg.C at a rate of 10 deg.C/min, and taking the peak temperature as melting temperature.
(2) Melt mass flow rate (melt index, MFR): measured according to standard ISO 1133, the experimental conditions: 2.16911 kg,190 ℃.
(3) 13 C-NMR measurement: performed in a deuterated o-dichlorobenzene solution of polymer (8-12 wt%) at 120 ℃ by using a 90 ° pulse, a 15s delay between pulse and CPD to remove 1 H- 13 C coupling, spectra were obtained on a Bruker AV-600 spectrometer operating at 150MHz according to the Fourier transform mode at 120 ℃ and nuclear magnetic calculations were performed with reference to Carbon-13NMR spectral analysis of stationary polymeric shifts and the polymerization mechanism.
(4) Oxidative Induction Time (OIT): the test was carried out using the ISO11357 standard, at a test temperature of 200 ℃.
Example 1
A mass polymerization method is adopted for polymerization, a 5L high-pressure-resistant stainless steel reaction kettle is heated to 75 ℃ in advance, and high-purity nitrogen is used for purging to remove air and trace water in the reaction kettle. Introducing hydrogen with the partial pressure of 0.1MPa into the reaction kettle, and stirring at the speed of 400rpm/min; adding 10mgMgCl into the reaction kettle 2 /TiCl 4 A mixture of a supported Ziegler-Natta catalyst, 3ml of a triethylaluminum solution (solvent is n-hexane) with the concentration of 1mol/L, 80ppm of an antioxidant AM1 (4,4' -bis (3,5-di-tert-butylbenzoylamino) diphenylmethane with the structure shown in formula (2-17)) (the molar ratio of triethylaluminum to the antioxidant AM1 is 1:5), and 3ml of dicyclopentyldimethoxysilane with the concentration of 0.1 mol/L; 3L of 1-butene monomer was added to the reactor. The reaction was carried out at a polymerization temperature of 75 ℃ for 1 hour with stirring at 500 rpm. After the reaction is finished, discharging the polymer into a device containing hot water, after the unreacted olefin monomer is basically volatilized, fully leaching the polymer with water, drying, weighing, characterizing and analyzing, and obtaining a polymer analysis resultAre shown in Table 1.
Example 2
Example 2 the catalyst, polymerization process conditions and adjuvant formulation used were the same as in example 1. The difference from example 1 is that: the hydrogen addition was varied and the partial pressure increased to 0.5MPa. The analysis results of the obtained polymer are shown in Table 1.
Example 3
Example 3 the catalyst, polymerization process conditions and adjuvant formulation used were the same as in example 1. The difference from example 1 is that: the hydrogen addition was varied and the partial pressure increased to 1.0MPa. The analysis results of the obtained polymer are shown in Table 1.
Example 4
Example 4 the catalyst, polymerization process conditions and adjuvant formulation used were the same as in example 1. The difference from example 1 is that: the antioxidant is replaced by AM2 (4,4' -di (3,5-di-tert-butylbenzoylamido) dimethyl ether with the same molar amount and has a structure shown in a formula (2-18)). The analysis results of the obtained polymer are shown in Table 1.
Example 5
Example 5 the catalyst, polymerization process conditions and adjuvant formulation used were the same as in example 1. The difference from example 1 is that: the antioxidant is replaced by AO18 (tetra (3,5-di-tert-butyl-4-hydroxy) phenylpropionic acid pentaerythritol ester with the structure shown in the formula (2-3)) with the same molar dosage. The analysis results of the obtained polymer are shown in Table 1.
Example 6
Example 6 the catalyst, polymerization process conditions and coagent formulation used were the same as in example 1. The difference from example 1 is that: the antioxidant was replaced with the same molar amount of AO13 (1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzene) -2,4,6-methylbenzene, having the structure shown in formula (2-14)). The analysis results of the obtained polymer are shown in Table 1.
Example 7
Example 7 the catalyst, polymerization process conditions and coagent formulation used were the same as in example 1. The difference from example 1 is that: the antioxidant was replaced with the same molar amount of AO80 (3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acrylic ] -1,1-dimethyl } -2,4,8,10-tetraoxaspiro undecane having the structure shown in formula (2-16)). The analysis results of the obtained polymer are shown in Table 1.
Example 8
Example 8 the catalyst, polymerization process conditions and coagent formulation used were the same as in example 1. The difference from example 1 is that: the antioxidant is replaced by 1024 (N, N' -bis [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine with the same molar amount, and the structure shown in the formula (2-4)) is obtained. The analysis results of the obtained polymer are shown in Table 1.
Example 9
Example 9 the catalyst, polymerization process conditions and coagent formulation used were the same as in example 1. The difference from example 1 is that: the antioxidant is replaced by 1076 (beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester with the structure shown in the formula (2-1)) with the same molar amount. The analysis results of the obtained polymer are shown in Table 1.
Example 10
Example 10 the catalyst, polymerization process conditions and coagent formulation used were the same as in example 1. The difference from example 1 is that: the triethylaluminum was exchanged for methylaluminoxane of the same concentration and volume. The analysis results of the obtained polymer are shown in Table 1.
Example 11
Example 11 the catalyst, polymerization process conditions and coagent formulation used were the same as in example 1. The difference from example 1 is that: the dicyclopentyldimethoxysilane was changed to cyclohexylmethyldimethoxysilane at the same concentration and volume, and the analytical results of the obtained polymer are shown in Table 1.
Example 12
Example 12 the catalyst, polymerization process conditions and coagent formulation used were the same as in example 1. The difference from example 1 is that: the antioxidant AM1 was used in an amount of 40ppm (molar ratio of triethylaluminum to antioxidant AM 1: 2.5), and the analytical results of the obtained polymer are shown in Table 1.
Example 13
Example 13 the catalyst, polymerization process conditions and coagent formulation used were the same as in example 1. The difference from example 1 is that: the amount of the antioxidant AM1 was changed to 160ppm (molar ratio of triethylaluminum to the antioxidant AM 1: 10), and the analysis results of the obtained polymer are shown in Table 1.
Comparative example 1
The polymerization was carried out by bulk polymerization, in which air and traces of water were removed from the polymerization vessel at 75 ℃. Adding hydrogen with partial pressure of 0.1MPa into the reaction kettle, and stirring at the speed of 400rpm/min; adding 10mgMgCl into the reaction kettle 2 /TiCl 4 A supported Ziegler-Natta catalyst, 3ml of triethyl aluminum with the concentration of 1mol/L and 3ml of dicyclopentyl dimethoxy silane with the concentration of 0.1mol/L without adding an antioxidant, and 3L of 1-butene monomer is introduced. The reaction was carried out at a polymerization temperature of 75 ℃ for 1 hour with stirring at 500 rpm. After the reaction was completed, the remaining reaction monomer was discharged to terminate the reaction, thereby obtaining a 1-butene polymer, and the analysis results of the polymer are shown in Table 1.
Comparative example 2
Comparative example 2 the catalyst, polymerization process conditions and adjuvant formulation used were the same as in comparative example 1. The difference from comparative example 1 is that: the hydrogen partial pressure was changed to 0.5MPa, and the analysis results of the obtained polymer are shown in Table 1.
Test example
To further illustrate the effect of adding an antioxidant during polymerization, the polymers obtained in examples 1-2 above were compared with those obtained in comparative examples 1-2 by heat treatment. Wherein, the polymer obtained in the example 1-2 is respectively cut into small blocks, antioxidant is not added, MFR is directly tested, and a sample strip is obtained; and the bars from the previous step are re-clipped for MFR testing and this step is repeated 5 times. The polymer obtained in the comparative example 1-2 is added with the antioxidant with the same proportion and the same type as the polymer obtained in the example 1-2, and then the mixture is stirred uniformly by a stirrer, and MFR is tested to obtain a sample strip; and the bars from the previous step are re-clipped for MFR testing and this step is repeated 5 times. The results obtained are shown in Table 2.
TABLE 1
Figure BDA0001838987610000191
TABLE 2
Figure BDA0001838987610000192
As can be seen from the results in Table 1, the Oxidation Induction Time (OIT) of the polymer is significantly increased and the oxidation resistance of the polymer is improved by the method of the present invention. In order to further verify the advantages of the olefin polymerization reaction provided by the invention, the polymer is subjected to multiple heat treatment experiments, the obtained results are shown in table 2, and as can be seen from the results in table 2, under the condition of the same antioxidant type and the same addition amount, the polymer obtained by the method provided by the invention has more excellent antioxidant capacity and can keep good thermal stability for a long time. In summary, the results in tables 1 and 2 strongly demonstrate that the olefin polymerization method provided by the present invention is beneficial to improve the oxidation resistance of the polymer and reduce the post-processing difficulty and cost.
While embodiments of the present invention have been described above, the above description is illustrative, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (18)

1. An olefin polymerization reaction comprising polymerizing an olefin in the presence of a Ziegler-Natta catalyst system, said olefin being 1-butene or a mixture of 1-butene and an alpha-olefin;
the Ziegler-Natta catalyst system comprises a component A, a component B and a component C, wherein the component A is a magnesium chloride supported Ziegler-Natta catalyst which contains Ti and an internal electron donor, the component B is a mixture of organic aluminum and an antioxidant, the molar ratio of the organic aluminum to the antioxidant is 1 (1-100), and the component C is an external electron donor; the concentration of the organic aluminum is 0.1-10mol/L, the organic aluminum is prepared by adopting an inert solvent for dilution, and the organic aluminum in the mixture reacts with the antioxidant to form a shielding body structure;
discharging the polymer obtained by the reaction into a device with hot water, leaching the polymer by using a compound containing hydroxyl after the unreacted olefin monomer is basically volatilized, and drying;
the antioxidant is selected from phenol antioxidants, and the phenol antioxidants are hindered phenol antioxidants with the structure shown in the formula (1):
Figure FDA0003973384230000011
wherein R is 1 And R 2 Each independently is a hydrogen atom, C 1 -C 5 Alkyl of (C) 5 -C 7 Cycloalkyl or C 7 -C 9 Is R is absent or is C 1 -C 8 N is an integer of 1 to 4, when n is 1, T represents C 1 -C 5 Alkyl of (C) 5 -C 7 Cycloalkyl or C 7 -C 9 When n is 2-4, T represents a direct bond, C 1 -C 30 Optionally heteroatom-substituted n-valent hydrogenated hydrocarbyl, ca, mg or S, X is a flexible structural unit, a benzene ring or a heterocyclic ring having a rigid structure, or a structural unit having both flexibility and rigidity;
the hydroxyl-containing compound is selected from water and alcohol.
2. The olefin polymerization reaction according to claim 1, wherein X has any one of the structures represented by the following formulae (1-1) to (1-11):
Figure FDA0003973384230000021
when n is 1, R 3 -R 5 Each of which isIndependently H, C 1 -C 18 Alkyl or a heterocyclic ring bonded to T; when n is 2-4, R 3 -R 5 Each independently H, C 1 -C 18 Alkyl of (a), a heterocyclic ring bonded to T or with another R 3 A heterocycle formed by the combination; r 6 Is absent or is C 1 -C 5 An alkylene group of (a); r 7 -R 9 Each independently is H or C 1 -C 5 The alkyl group of (1).
3. The olefin polymerization reaction according to claim 2, wherein the hindered phenolic antioxidant is at least one selected from the group consisting of compounds represented by the following formulae (2-1) to (2-18):
Figure FDA0003973384230000031
Figure FDA0003973384230000041
Figure FDA0003973384230000051
Figure FDA0003973384230000061
4. the olefin polymerization reaction according to claim 1, wherein the molar ratio of the component A to the component B is 1 (10-500) in terms of titanium/aluminum; the molar ratio of the component C to the component B calculated as aluminum is (0.005-0.5): 1.
5. The olefin polymerization reaction according to claim 4, wherein the molar ratio of the component A to the component B is 1 (25-100) in terms of titanium/aluminum; the molar ratio of the component C to the component B calculated as aluminum is (0.01-0.4): 1.
6. The olefin polymerization reaction of claim 1, wherein the internal electron donor in the component A is at least one selected from the group consisting of carboxylic acid ester compounds, ether compounds, 1,3-alcohol ester compounds and sulfonamide compounds;
the organic aluminum is aluminum hydroxide having AlR n X (3-n) An alkylaluminum compound of the structure and/or an alkylaluminoxane, R is C 1 -C 20 Alkyl radical, C 7 -C 20 Aralkyl or C 6 -C 20 Aryl, X is halogen, and n is an integer of 0 to 3;
the external electron donor is at least one selected from siloxane compounds, amino silane compounds, organic amine compounds and ether compounds.
7. The olefin polymerization reaction of claim 6, wherein said compound has AlR n X (3-n) The alkylaluminum compound of structure (la) is selected from at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-butylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, dimethylaluminum monochloride, diisobutylaluminum monochloride, isobutylaluminum dichloride, tris (2-methyl-3-phenyl-butyl) aluminum and tris (2-phenyl-butyl) aluminum.
8. The olefin polymerization reaction of claim 6, wherein the alkylaluminoxane is selected from at least one of methylaluminoxane, tetra (isobutyl) aluminoxane, tetra (2,4,4-trimethyl-pentyl) aluminoxane, tetra (2,3-dimethylbutyl) aluminoxane, and tetra (2,3,3-trimethylbutyl) aluminoxane.
9. The olefin polymerization reaction according to claim 6, wherein the siloxane-based compound is at least one selected from the group consisting of trimethylmethoxysilane, trimethylethoxysilane, methyl-t-butyldimethoxysilane, cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, dicyclopentyldimethoxysilane, isobutylcyclohexyldimethoxysilane, tetraethoxysilane and n-propenotriethoxysilane.
10. The olefin polymerization reaction according to claim 6, wherein the aminosilane-based compound is at least one selected from the group consisting of diethylaminotriethoxysilane, 3-aminopropyltriethoxysilane, diethylaminomethyltriethoxysilane, dimethylaminomethyltriethoxysilane, diisopropylaminomethyltriethoxysilane, di-n-propylaminomethyltriethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, piperidinyltriethoxysilane and pyrrolyltriethoxysilane.
11. The olefin polymerization reaction according to claim 6, the organic amine compound is selected from aziridine, azetidine, pyrrolidine, azepane, azocane, 2,3-dimethyl aziridine, 2,3-tetramethyl azetidine, 2,3-tetraethylazetidine, 2,3-tetramethyl pyrrolidine, 2,3-tetra-n-propyl pyrrolidine, 2,3-tetraisopropyl pyrrolidine, 2,3-tetraisobutyl pyrrolidine, 2,3-tetramethyl piperidine, 58 zxft Piperidine, 2,3-tetraethylpiperidine, 2,3-tetra-n-propyl piperidine 2,3-tetraisopropylpiperidine, 2,3-tetraisobutylpiperidine, 2,3-tetramethylpiperidine, 2,3-tetraethylpiperidine, 2-methyl-2-cyclohexyl-6-methyl-6-ethylpiperidine, 2,3-dicyclopentyl-2,3-dimethylpiperidine, 2,3-tetramethylazepane, 2,3-tetraethylazepane, 2,3-tetra-n-propylazepane, 2,3-tetraisopropylazepane, 58 zxft 6258-tetraisobutylazepane, 2,3-tetramethylazepane, 2,3-tetraethylazepane, 58 zxft 6258-tetramethylazepane, 2,3-tetramethyl6258-tetraethyl 627-methyl-6258-tetraethylazepane, 6258-tetraethyl-2-ethylcycloheptane, 2,3-tetraethyl-ethylcycloheptane, 6258-tetramethylazepane, 2,2-dicyclopentyl-7,7-dimethylazacycloheptane, 2,2,8,8-tetramethylazocane, 2,2,8,8-tetraethylazocane, 2,2,8,8-tetra-n-propylazocane, 2,2,8,8-tetraisopropylazocane, 2,2,8,8-tetra-n-butyl azocane, 2,2,8,8-tetraisobutylazocane, 2,2,7,7-tetramethylazocane, 2,2,6,6-tetramethylazocane, 3,3,5,5-tetramethylazocane, and 3,3,6,6-tetramethylazocane.
12. The olefin polymerization reaction according to claim 6, wherein the ether-based compound is at least one compound selected from the group consisting of compounds of the following general formulae:
Figure FDA0003973384230000091
wherein R is 1 And R 2 Each independently selected from C 1 -C 20 One of linear, branched or cyclic aliphatic radicals, R 3 、R 4 、R 5 、R 6 、R 7 And R 8 Each independently selected from a hydrogen atom, a halogen atom, C 1 -C 20 Straight or branched alkyl of (2), C 3 -C 20 Cycloalkyl radical, C 6 -C 20 Aryl radical, C 7 -C 20 Alkylaryl and C 7 -C 20 One of aralkyl, and R 3 、R 4 、R 5 、R 6 、R 7 And R 8 Optionally linked to form a ring.
13. The olefin polymerization reaction according to claim 12, the ether compound is selected from 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-phenyl-1,3-dimethoxypropane, 2,2-benzyl-1,3-dimethoxypropane, 2-isopropyl-2-isoamyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-isopropyl-2-3,7-dimethyloctyl-dimethoxypropane, 2,2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 5852 zxft 3552-35zzft 3552-dipropyloxy-3575-dipropyloxy-propane, dipropyl-3625-isopropyloxy-3625-isopropyloxy-3428-dipropyloxy-3625-propyl-3625-diethoxypropane and bis (cyclohexyloxy-3625-diethoxypropane.
14. The olefin polymerization reaction according to claim 1, wherein the organoaluminum has a concentration of 0.5 to 5mol/L.
15. The olefin polymerization reaction according to any one of claims 1-14, wherein the olefin polymerization reaction comprises:
s1, heating a polymerization reaction kettle and purging with nitrogen to remove air and trace water in the polymerization reaction kettle;
s2, introducing hydrogen and the Ziegler-Natta catalyst system into the polymerization reaction kettle;
s3, adding the olefin into the polymerization reaction kettle, controlling the stirring speed to be 400-600rpm/min, reacting for 0.5-3h at 20-100 ℃, and stopping the reaction;
and S4, discharging the obtained polymer into a device with hot water, leaching the polymer by using a hydroxyl-containing compound after the unreacted olefin monomer is basically volatilized, and drying.
16. A polyolefin produced by the olefin polymerization reaction of any one of claims 1-15.
17. The polyolefin of claim 16, wherein the polyolefin has a mole content of α -olefin derived units of 0.1 to 30% based on the total mole amount of olefin derived units, an antioxidant content of 40ppm or more, and a melt index of 0.1 to 1000g/10min at 190 ℃ under 2.16 kg.
18. The polyolefin of claim 17 wherein the antioxidant is present in the polyolefin in an amount of 40 to 2000ppm.
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CN1033060A (en) * 1987-11-13 1989-05-24 壳牌石油公司 The preparation method of stable olefin compound
CN1231292A (en) * 1998-04-03 1999-10-13 中国石油化工总公司 Process for preparing stable polyolefine
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