CN114516930A - Ethylene polymerization process and ethylene polymers made therefrom - Google Patents
Ethylene polymerization process and ethylene polymers made therefrom Download PDFInfo
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- CN114516930A CN114516930A CN202011314968.3A CN202011314968A CN114516930A CN 114516930 A CN114516930 A CN 114516930A CN 202011314968 A CN202011314968 A CN 202011314968A CN 114516930 A CN114516930 A CN 114516930A
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Abstract
The invention discloses an ethylene polymerization method and an ethylene copolymer prepared by the method, and the method comprises the step of contacting ethylene and conjugated diene in the presence of a polymerization catalyst, wherein the polymerization catalyst comprises a component A and a component B, the component A is selected from metal compounds shown in a formula 1, and the component B is an organic aluminum compound and/or an organic boron compound. According to the ethylene polymerization method of the present invention, an ethylene copolymer having a higher content of a conjugated diene structural unit can be prepared with a higher catalytic activity, and the polymer main chain of the prepared ethylene copolymer contains no or substantially no unsaturated bond, and the molecular weight distribution of the prepared ethylene copolymer is narrow.
Description
Technical Field
The present invention relates to an ethylene polymerization process and an ethylene polymer prepared by the process, and particularly, to a polymerization process of ethylene and conjugated diene and an ethylene polymer prepared by the process.
Background
Ethylene is widely used in the plastics industry as a monomer which is used in large quantities and is readily available. Conjugated dienes, particularly butadiene and isoprene, are the most important monomers for the synthesis of rubber. Butadiene, a by-product of the petroleum route to ethylene, was once at a price similar to ethylene. Recently, the price of butadiene has increased dramatically due to the decrease in the production of butadiene resulting from the change in the ethylene production route. In contrast, the price of ethylene is reduced. Therefore, the use of ethylene as a raw material for the production of rubber for tires is attractive, and the raw material cost can be greatly saved.
However, copolymerization is difficult due to the difference in polymerization mechanism between the conjugated diene and the α -olefin, which results in difficulty in increasing the content of the structural unit derived from the conjugated diene in the copolymer to be prepared and the molecular weight of the copolymer, and results in low activity of the catalyst, low production efficiency, and difficulty in meeting the requirements of mass production. Meanwhile, from the viewpoint of application, it is also required to reduce the content of unsaturated bonds in the main chain of the polymer to improve physical properties such as weather resistance, heat resistance and ozone resistance of the copolymer.
Therefore, the copolymerization of ethylene and conjugated diene by using the same catalytic system is a very challenging subject, the realization of the copolymerization of ethylene and conjugated diene has been the direction of the academic and industrial efforts, and the development of a polymerization method suitable for the copolymerization of ethylene and conjugated diene has important significance.
Disclosure of Invention
The invention aims to provide an ethylene polymerization method, which can obtain higher catalytic activity when polymerizing ethylene and conjugated diene, can improve the content and molecular weight of structural units derived from the conjugated diene in the prepared ethylene copolymer, and simultaneously has low content of unsaturated bonds on the main chain of the prepared ethylene copolymer.
According to a first aspect of the present invention, there is provided an ethylene polymerization process comprising contacting ethylene with a conjugated diene in the presence of a polymerization catalyst comprising component A and component B,
the component A is selected from metal compounds shown in a formula 1,
in formula 1, M is a metal atom selected from groups IB, IIIB, IVB, VB, VIB, VIIB and VIII,
X1and X2Identical or different, each independently a halogen atom,
rb is a divalent group of a group IIIA element, a divalent group of a group IVA element, a divalent group of a group VA element or a divalent group of a group VIA element,
L1and L2The same or different, each independently selected from the group represented by formula 2 to formula 8, and L1And L2Is not the formula 6, the formula 7 or the formula 8 at the same time,
R1、R2、R3、R4、R5、R6、R7、R8and R9The same or different, each independently is a hydrogen atom, C1-C20Alkyl or C6-C20Aryl of (a);
the component B is an organic aluminum compound and/or an organic boron compound.
According to a second aspect of the present invention there is provided an ethylene copolymer produced by the process of the first aspect of the present invention.
According to the ethylene polymerization method, the ethylene copolymer with higher conjugated diene structural unit content and higher molecular weight can be prepared with higher catalytic activity, the polymer main chain of the prepared ethylene copolymer does not contain or basically does not contain unsaturated bonds, and the prepared ethylene has narrow molecular weight distribution. The ethylene polymerization process according to the present invention has a wide application prospect.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the present invention, there is provided an ethylene polymerization process comprising contacting ethylene with a conjugated diene in the presence of a polymerization catalyst comprising component a and component B.
The component A is selected from metal compounds shown in a formula 1,
in formula 1, M is a metal atom selected from groups IB, IIIB, IVB, VB, VIB, VIIB, and VIII, preferably a metal element selected from group IVB, and may be, for example, a titanium atom, a zirconium atom, or a hafnium atom, and more preferably a zirconium atom.
In formula 1, X1And X2The same or different, each independently is a halogen atom. Preferably, in formula 1, X1And X2Are all chlorine atoms.
In formula 1, Rb is a divalent group of a group IIIA element, a divalent group of a group IVA element, a divalent group of a group VA element, or a divalent group of a group VIA element. Preferably, Rb is a divalent group of a group IVA element. More preferably, Rb is a divalent group represented by formula 14,
in the formula 14, R1And R2Identical or different, each independently is C1-C10Alkyl group of (1). C1-C10Alkyl of (2) includes C1-C10Straight chain alkyl group of (1), C3-C10Branched alkyl and C3-C10Specific examples thereof may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl and its various isomers, hexyl and its various isomers, heptyl and its various isomers, octyl and its various isomers, nonyl and its various isomers, and decyl and its various isomers. Preferably, in formula 14, R1And R2Each independently is C1-C6Alkyl group of (1). More preferably, in formula 14, R1And R2Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl. Further preferably, in formula 14, R1And R2Is methyl.
In the formula 1, L1And L2The same or different, each independently selected from the group represented by formula 2 to formula 8, and L1And L2Is not the formula 6, the formula 7 or the formula 8 at the same time,
R1、R2、R3、R4、R5、R6、R7、R8and R9The same or different, each independently is a hydrogen atom, C1-C20Alkyl or C6-C20Aryl group of (1).
In the present invention, C1-C20Alkyl of (2) includes C1-C20Straight chain alkyl group of (1), C3-C20Branched alkyl and C3-C20Specific examples thereof may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl and its various isomers, hexyl and its various isomers, heptyl and its various isomers, octyl and its various isomers, nonyl and its various isomers, decyl and its various isomers, undecyl and its various isomers, dodecyl and its various isomers, tridecyl and its various isomers, tetradecyl and its various isomers, pentadecyl and its various isomers, hexadecyl and its various isomers, heptadecyl and its various isomers, octadecyl and its various isomers, nonadecyl and its various isomers, and eicosyl and its various isomers.
In the present invention, C6-C20Specific examples of the aryl group of (a) may include, but are not limited to: phenyl, tolyl, ethylphenyl, propylphenyl (wherein propyl may be n-propyl or isopropyl), butylphenyl (wherein butyl may be n-butyl, sec-butyl, isobutyl or tert-butyl), naphthyl, anthryl or phenanthryl.
Preferably, R1、R2、R3、R4、R5、R6、R7、R8And R9Each independently is a hydrogen atom, C1-C10Alkyl or C6-C20Aryl group of (1). More preferably, R1、R2、R3、R4、R5、R6、R7、R8And R9Each independently is a hydrogen atom, C1-C5Alkyl or C6-C20Aryl group of (1). Further preferably, R1、R2、R3、R4、R5、R6、R7、R8And R9Each independently is a hydrogen atom, a methyl group, a ethyl groupA radical, n-propyl, isopropyl, phenyl, anthryl or phenanthryl.
For the group of formula 2, in a preferred embodiment, R1、R2、R3、R4And R5Preferably both are hydrogen atoms.
For the group of formula 3, in a preferred embodiment, R2And R4Identical or different, preferably each independently of the others, is C1-C20More preferably each independently is C1-C10Further preferably each independently of the other is C1-C5Even more preferably each independently is C1-C4Particularly preferably each independently of the other is hydrogen, methyl, ethyl, n-propyl or isopropyl, R1、R3And R5Is a hydrogen atom.
For the group of formula 4, in a preferred embodiment, R1And R4Preferably C1-C20More preferably C1-C10Further preferably C1-C5More preferably methyl, ethyl, n-propyl or isopropyl, R2Preferably C6-C20More preferably C6-C15Further preferably phenyl, anthryl or phenanthryl, R3Is hydrogen.
According to the process of the invention, in formula 1, L1And L2Preferably each independently selected from the group represented by formula 2 to formula 5. According to the process of the present invention, in formula 1, L1And L2Preferably the same group, more preferably the same group and is a group represented by formula 2, a group represented by formula 3, a group represented by formula 4 or a group represented by formula 5.
According to the process of the present invention, in a preferred embodiment, the component A is selected from metal compounds represented by formula 9 to formula 13,
according to this preferred embodiment, in a more preferred example, the component a is a metal compound represented by formula 13. According to this preferred embodiment, the method according to the invention allows to obtain a significantly improved catalytic activity and thus an improved production efficiency. Meanwhile, the polymer main chain of the ethylene polymer prepared according to this more preferred embodiment is substantially free of unsaturated groups.
According to this preferred embodiment, in another more preferred example, the component a is a metal compound represented by formula 11 or formula 12. According to the preferred embodiment, the polymerization catalyst has more balanced catalytic performance, not only can obtain higher catalytic activity, but also can obtain higher conjugated diene combining capacity, and the prepared ethylene copolymer has higher conjugated diene structural unit content, higher molecular weight and narrow molecular weight distribution, and the polymer main chain of the prepared ethylene copolymer does not contain unsaturated groups basically.
According to this preferred embodiment, in yet another more preferred example, the component a is a metal compound represented by formula 9 or formula 10. According to the more preferable embodiment, a higher conjugated diene binding ability can be obtained, and the content of a group having a double bond in a side chain formed by 1, 2-polymerization of the conjugated diene is higher.
The metal compounds of component A are commercially available according to the process of the present invention, and can also be prepared by conventional methods.
According to the process of the present invention, the component B is an organoaluminum compound and/or an organoboron compound.
The organoaluminum compound may be an aluminoxane and/or a hydrocarbylaluminum.
In one embodiment, the organoaluminum compound aluminoxane is preferably Methylaluminoxane (MAO).
In another embodiment, the organoaluminum compound is a compound represented by formula 15,
in the formula 15, R3、R4And R5Are the same or different and are each independently selected from C1-C10Alkyl of (C)1-C10Alkoxy group of (C)6-C20Aryl of (C)7-C15Alkylaryl of, C7-C15Aralkyl and hydrogen atom of (2), and R3、R4And R5Not simultaneously hydrogen atoms.
C1-C10Is alkyl including C1-C10Straight chain alkyl of (1), C3-C10Branched alkyl and C3-C10Specific examples thereof may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl and its various isomers, hexyl and its various isomers, heptyl and its various isomers, octyl and its various isomers, nonyl and its various isomers, decyl and its various isomers, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
Said C is1-C10Specific examples of the alkoxy group of (b) may include, but are not limited to: methoxy, ethoxy, propoxy and butoxy.
Said C is6-C20Specific examples of the aryl group of (a) may include, but are not limited to: phenyl, tolyl, ethylphenyl, propylphenyl (wherein propyl may be n-propyl or isopropyl), butylphenyl (wherein butyl may be n-butyl, sec-butyl, isobutyl or tert-butyl), naphthyl, anthryl or phenanthryl.
The alkylaryl group means an aryl group having an alkyl substituent, and specific examples of the alkylaryl group may include, but are not limited to: tolyl, ethylphenyl, dimethylphenyl, and diethylphenyl.
The aralkyl group means an alkyl group having an aryl substituent, and specific examples of the aralkyl group may include, but are not limited to: benzyl, phenethyl, 1-phenylpropyl, 2-phenylpropyl and 3-phenylpropyl.
Specific examples of the alkyl aluminum compound may include, but are not limited to: diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, ethylaluminum dihydride, butylaluminum dihydride, isobutylaluminum dihydride, octylaluminum dihydride, pentylaluminum dihydride, diethylaluminum ethoxide, dipropylaluminum ethoxide, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldiphenylaluminum, triisopropylaluminum, ethyl di-p-tolylaluminum, ethyl dibenzylaluminum, diethyl phenylaluminum, diethyl p-tolylaluminum, and diethyl benzylaluminum.
In a preferred embodiment, in formula 15, R3、R4And R5Is methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl. More preferably, in formula 15, R3、R4And R5Are all isobutyl.
According to the production method of the present invention, the organoaluminum compound is preferably methylaluminoxane and/or triisobutylaluminum.
The organoboron compound is preferably an organoborate. The organic borate is an ionic compound consisting of borate anions and cations.
Specific examples of the borate anion may include, but are not limited to: tetraphenyl borate, tetrakis (mono-fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetrakis (tolyl) borate, tetraxylyl borate, (triphenyl-pentafluorophenyl) borate, [ tris (pentafluorophenyl) phenyl ] borate, and undecahydro-7, 8-dicarbaundecaborate.
Specific examples of the cation may include, but are not limited to: carbonium cations, oxonium cations, ammonium cations, phosphine cations, cycloheptatrienyl cations, and ferrocenium cations containing transition metals. Wherein the carbonium cation comprises a trisubstituted carbonium cation, such as triphenylcarbonium cation and tris (substituted phenyl) carbonium cation. More specific examples of the tri (substituted phenyl) carbonium cation include a tri (tolyl) carbonium cation. Specific examples of ammonium cations may include, but are not limited to: trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; n, N-dialkylanilinium cations, such as N, N-dimethylanilinium cation, N-diethylanilinium cation and N, N-2,4, 6-pentamethylanilinium cation; and dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation. Specific examples of phosphine cations may include, but are not limited to: triaryl cations such as triphenylphosphine cation, tri (tolyl) phosphine cation and tri (xylyl) phosphine cation.
According to the process of the present invention, the organoboron compound is preferably trityl-tetrakis (pentafluorophenyl) borate. The organoboron compound is preferably used in combination with the aluminum hydrocarbyl.
According to the process of the invention, the molar ratio of said component a to said component B may be 1: 0.1 to 5000, preferably 1: 1-3000, more preferably 1: 1 to 1000, more preferably 1: 10-1000, more preferably 1: 100-800. When the component B is an organoaluminum compound and an organoboron compound, the molar ratio of the organoaluminum compound to the organoboron compound can be from 0.1 to 1000: 1, preferably 1 to 500: 1, more preferably 10 to 300: 1, more preferably 40 to 100: 1.
according to the process of the present invention, said component A is used in an amount of 0.1 to 100. mu. mol, preferably 1 to 80. mu. mol, more preferably 5 to 60. mu. mol, still more preferably 6 to 30. mu. mol, relative to 1mol of the conjugated diene.
According to the method of the present invention, in a preferred embodiment, the component a is a metal compound represented by formula 9 to formula 13, and the component B is an aluminoxane, preferably methylaluminoxane. According to this preferred embodiment, the ethylene copolymer produced has not only a high content of conjugated diene structural units but also a high content of 1, 2-polymerized vinyl structural units, while the content of unsaturated double bonds in the main chain of the copolymer is low. According to this preferred embodiment, the ethylene copolymer produced has good crosslinking properties, and the crosslinked product is good in weather resistance, heat resistance and ozone resistance. According to this preferred embodiment, said component A is preferably used in an amount of 6.5 to 20. mu. mol, more preferably 7 to 15. mu. mol, relative to 1mol of conjugated diene.
According to the process of the present invention, the contacting of ethylene with conjugated diolefin may be carried out at a temperature of from-50 ℃ to 150 ℃, preferably at a temperature of from 10 ℃ to 120 ℃, more preferably at a temperature of from 30 ℃ to 90 ℃, even more preferably at a temperature of from 40 ℃ to 70 ℃. In the process of the present invention, when ethylene is contact-polymerized with a conjugated diene, the pressure of ethylene may be from 0 to 100MPa, preferably from 2 to 50MPa, more preferably from 3 to 30MPa, further preferably from 5 to 10MPa, in terms of gauge pressure (G).
According to the process of the invention, the contacting is carried out in the presence of a molecular weight regulator. The molecular weight regulator may be of conventional choice, preferably hydrogen. The ethylene copolymer prepared by the method has higher molecular weight. Generally, the olefin polymer produced according to the process of the present invention may have a number average molecular weight (in g/mol) of 10,000 or more, preferably 12,000 to 500,000, more preferably 14,000 to 400,000, further preferably 16,000 to 350,000, still further preferably 20,000 to 320,000.
The process according to the invention can be carried out by solution polymerization. In solution polymerization, solvents that may be employed include C6-C12Aromatic hydrocarbon solvent, C6-C12Halogenated aromatic hydrocarbon of (1), C5-C10Linear alkane of (1) and C5-C10Cycloalkane of (2)For example: one or more of toluene, chlorobenzene, dichlorobenzene, n-hexane and cyclohexane.
According to the process of the present invention, the conjugated diene refers to a compound having a conjugated double bond in its molecular structure. Specific examples of the conjugated diene may include, but are not limited to, butadiene and/or isoprene.
According to a second aspect of the present invention there is provided an ethylene copolymer produced by the process of the first aspect of the present invention.
The ethylene copolymer prepared by the method has higher conjugated diene structure unit content, the main chain of the prepared ethylene copolymer does not contain or basically does not contain unsaturated bonds, and the prepared ethylene copolymer has narrow molecular weight distribution and high molecular weight.
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
In the following examples and comparative examples, the molecular weight and molecular weight distribution index (M) of the polymerw/Mn) The measurement was carried out by 1260 Infinity II high temperature gel permeation chromatograph manufactured by Agilent corporation using 2 columns (300X 7.5mm) of MIXD-B and 1 column (50X 7.5mm) of Guard. The mobile phase is trichlorobenzene, and the flow rate is 1 mL/min; the concentration of the sample solution is 0.1mg/mL, and the sample injection amount is 200 mu L; the test temperature is 150 ℃; monodispersed polystyrene was used as a standard.
In the following examples and comparative examples, the microstructure of the polymer was measured using a 400MHz NMR spectrometer commercially available from Bruke, using deuterated o-dichlorobenzene as a solvent and Tetramethylsilicon (TMS) as an internal standard. Wherein "conjugated diene structural unit" means a structural unit formed from a conjugated diene, "1, 2-polymerization" means that the conjugated diene is polymerized in a 1, 2-addition manner, "1, 4-polymerization" means that the conjugated diene is polymerized in a 1, 4-addition manner, "1, 3-polymerization" means that the conjugated diene is polymerized in a 1, 3-addition manner; "vinyl" refers to a structural unit of a conjugated diene formed by 1, 2-polymerization and having a pendant double bond(in the case of butadiene, vinyl is
"cyclopropane ring" means a structural unit in which a conjugated diene is formed by 1, 2-polymerization and which has a cyclopropane ring (in the case of butadiene, the cyclopropane ring is
"Cyclopentane ring" means a structural unit in which a conjugated diene is formed by 1, 2-polymerization and has a cyclopentane ring (in the case of butadiene, the cyclopentane ring is
The following examples and comparative examples relate to the following metal compounds.
Preparation examples 1 to 5 were used for preparing metal compounds 1 to 5.
Preparation example 1
Synthesis of Metal Compound 1
0.94g (2mmol) of bis (2, 5-dimethylcyclopentylthiophene) -dimethylsilyl and 50mL of diethyl ether are placed in a reaction flask and 2.5mL (4mmol) of a 1.6M solution of butyllithium in hexane are added dropwise at-78 ℃. After stirring at room temperature (25 ℃ C.) for 6 hours, the temperature was reduced to-40 ℃ C and 0.466g (2mmol) of zirconium tetrachloride was slowly added. Stir overnight. Filter and wash the solid with ether. The product was recrystallized from dichloromethane. Yield: 45% by weight.
H1-NMR(CDCl3,400MHz)：δppm 6.75(q,4H)，2.51(d,12H)，1.82(s,6H)。
Preparation example 2
Synthesis of Metal Compound 4
The same synthesis method as that of the metal compound 1 is adopted, except that the bis (2, 5-dimethylcyclopentylthiophene) -dimethyl silicon is replaced by 2mmol of bis (cyclopentylthiophene) -dimethyl silicon. Yield: 57% by weight.
H1-NMR(CDCl3,400MHz)：δppm 7.15(d,4H)，7.10(d,4H)，1.80(s,6H)。
Preparation example 3
And (3) synthesizing a metal compound 5.
1.02g (2mmol) of bis (2, 5-dimethyl-3-phenyl-6-hydro-cyclopenta [2,3-b ] thiophene-6) -dimethylsilyl-ene and 50mL of diethyl ether are introduced into a reaction flask and 2.5mL (4mmol) of 1.6M butyllithium hexane solution are added dropwise at-78 ℃. After stirring at room temperature (25 ℃ C.) for 6 hours, 0.466g (2mmol) of zirconium tetrachloride was slowly added. Stir overnight. Filter and wash the solid with ether. And (4) draining the filtrate to obtain a target product. Yield: 45% by weight.
H1-NMR(CD2Cl2,400MHz)：δppm 7.2-7.6(m,10H)，6.60(s，2H)，2.58(s，6H)，2.3(s，6H)，1.05(s，6H)。
Preparation example 4
Synthesis of Metal Compound 2
The same synthesis as for metal compound 5 was used, except that 2mmol of bis (2, 5-dimethyl-3-phenyl-6-hydro-cyclopenta [2,3-b ] thiophene-6) -dimethylsilyl group was used instead of bis (2, 5-dimethyl-3-phenyl-6-hydro-cyclopenta [2,3-b ] thiophene-6) -dimethylsilyl group. Yield: 56% by weight.
H1-NMR(CDCl3,400MHz)：δppm 7.15-8.90.(m,18H)，6.62(s，2H)，1.15-2.95(m，14H)，1.08(s，6H)，0.92(t,6H)。
Preparation example 5
Synthesis of Metal Compound 3
The same synthesis as for metal compound 5 was used, except that 2mmol of bis (2, 5-dimethyl-3-phenyl-6-hydro-cyclopenta [2,3-b ] thiophene-6) -dimethylsilyl was used instead of bis (2, 5-dimethyl-3-phenyl-6-hydro-cyclopenta [2,3-b ] thiophene-6) -dimethylsilyl. Yield: 61 wt%.
H1-NMR(CDCl3,400MHz)：δppm 7.10-8.85(m,18H)，6.60(s，2H)，1.85-2.80(m，10H)，1.10(s，6H)，0.85(s，6H)。
Examples 1-12 are intended to illustrate the ethylene polymerization process according to the invention.
Example 1
A500 mL stainless steel reactor was sufficiently purged with nitrogen and then purged with hydrogen, and 120g of toluene, 8mL of methylaluminoxane (10% by weight toluene solution), 25.0g of butadiene and 0.44kg/cm of butadiene were added2G hydrogen. At 60 ℃ with 7.8kg/cm2G ethylene saturates the liquid and gas phases. Thereafter, 5. mu. mol of the metal compound 1 dissolved in toluene in advance was added to start the polymerization. Ethylene gas was continuously supplied so that the total pressure was maintained at 7.8kg/cm2G. After 15 minutes of polymerization, the reaction was terminated by adding a small amount of methanol. The product was precipitated by pouring into a large amount of ethanol with hydrochloric acid (HCl concentration 2% by weight), the solid was separated by filtration, and the separated solid was washed with ethanol. The washed solid was dried in a vacuum oven until the weight was no longer reduced to give an ethylene copolymer according to the present invention. Specific experimental conditions are listed in table 1 and the results of the property parameter tests of the prepared ethylene copolymers are listed in table 2.
Example 2
An ethylene copolymer was prepared in the same manner as in example 1, except that methylaluminoxane was not used, but 2.5mL of a triisobutylaluminum in n-hexane solution (concentration of triisobutylaluminum is 1M) was used, and 0.03mmol of trityl-tetrakis (pentafluorophenyl) borate was dissolved in toluene together with the metal compound 1 and added to the polymerization reaction vessel. Specific experimental conditions are listed in table 1 and the results of the property parameter tests of the prepared ethylene copolymers are listed in table 2.
Comparative example 1
An ethylene copolymer was prepared in the same manner as in example 2, except that the metal compound 1 was replaced with the comparative metal compound 1. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Comparative example 2
An ethylene copolymer was prepared in the same manner as in example 1, except that the metal compound 1 was replaced with the comparative metal compound 1. The specific experimental conditions are listed in table 1 and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Example 3
An ethylene copolymer was prepared in the same manner as in example 1, except that: the metal compound 1 was replaced with the metal compound 2, and the properties of the ethylene copolymer obtained were as listed in Table 2.
Example 4
An ethylene copolymer was prepared in the same manner as in example 3, except that methylaluminoxane was not used, but 2.5mL of a triisobutylaluminum in n-hexane solution (concentration of triisobutylaluminum is 1M) was used, and 0.03mmol of trityl-tetrakis (pentafluorophenyl) borate was dissolved in toluene together with the metal compound 2 and added to the polymerization reaction vessel. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Comparative example 3
An ethylene copolymer was produced in the same manner as in example 3, except that the metal compound 2 was replaced with the comparative metal compound 2. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Example 5
A500 mL stainless steel autoclave was fully purged with nitrogen and then purged with hydrogen, and 120g of toluene, 7.5mL of MAO (10 wt% toluene solution), 35g of butadiene were added thereto, followed by addition of 0.44kg/cm2G hydrogen gas, 7.8kg/cm at 60 DEG C2G ethylene saturates the liquid and gas phases. Thereafter, 5. mu. mol of the metal compound 2 dissolved in toluene in advance was added to start the polymerization. Ethylene gas was continuously supplied so that the total pressure was maintained at 7.8kg/cm2G. After 15 minutes of polymerization, the reaction was terminated by adding a small amount of methanol. The product is poured into a large amount of ethanol (2% by weight, hydrochloric acid in HCl) with hydrochloric acid, precipitated, filtered to separate the copolymer, and washed with ethanol. Drying in a vacuum oven until the weight is no longer reduced gives the ethylene copolymer according to the invention. The specific experimental conditions are listed in Table 1, the testing of the Property parameters of the ethylene copolymers obtainedThe results are listed in table 2.
Comparative example 4
An ethylene copolymer was prepared in the same manner as in example 5 except that the metal compound 2 was replaced with the comparative metal compound 2. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Example 6
An ethylene copolymer was prepared in the same manner as in example 1, except that the metal compound 1 was replaced with the metal compound 3. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Example 7
An ethylene copolymer was prepared in the same manner as in example 6, except that methylaluminoxane was not used, but 2.5mL of a triisobutylaluminum in n-hexane solution (concentration of triisobutylaluminum is 1M) was used, and 0.03mmol of trityl-tetrakis (pentafluorophenyl) borate was dissolved in toluene together with the metal compound 3 and added to the polymerization reaction vessel. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Comparative example 5
An ethylene copolymer was prepared in the same manner as in example 6, except that the metal compound 3 was replaced with the comparative metal compound 3. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Comparative example 6
An ethylene copolymer was prepared in the same manner as in example 6, except that the metal compound 3 was replaced with the comparative metal compound 3. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Example 8
An ethylene copolymer was prepared in the same manner as in example 1, except that the metal compound 1 was replaced with a metal compound 4. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Example 9
An ethylene copolymer was prepared in the same manner as in example 8, except that methylaluminoxane was not used, but 2.5mL of a triisobutylaluminum in n-hexane solution (concentration of triisobutylaluminum is 1M) was used, and 0.03mmol of trityl-tetrakis (pentafluorophenyl) borate was dissolved in toluene together with the metal compound 4 and added to the polymerization reaction vessel. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Comparative example 7
An ethylene copolymer was produced in the same manner as in example 8 except that the metal compound 4 was replaced with the comparative metal compound 4. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Example 10
An ethylene copolymer was prepared in the same manner as in example 1, except that the metal compound 1 was replaced with a metal compound 4. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Comparative example 8
An ethylene copolymer was produced in the same manner as in example 9 except that the metal compound 4 was replaced with the comparative metal compound 6. The specific experimental conditions are listed in table 1 and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Comparative example 9
An ethylene copolymer was produced in the same manner as in example 9 except that the metal compound 4 was replaced with the comparative metal compound 7. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Example 11
An ethylene copolymer was prepared in the same manner as in example 1, except that the amount of butadiene was changed and the metal compound 1 was replaced with the metal compound 5, and the results of the property parameter tests of the prepared ethylene copolymer are shown in Table 2.
Comparative example 10
An ethylene copolymer was prepared in the same manner as in example 11 except that the metal compound 5 was replaced with the comparative metal compound 5, and the results of the property parameter tests of the ethylene copolymer obtained were as shown in Table 2.
Example 12
An ethylene copolymer was prepared in the same manner as in example 1, except that the amount of butadiene was changed and the metal compound 1 was replaced with the metal compound 5, and the results of the property parameter tests of the prepared ethylene copolymer are shown in Table 2.
Comparative example 11
An ethylene copolymer was prepared in the same manner as in example 12 except that the metal compound 5 was replaced with the comparative metal compound 5, and the results of the property parameter tests of the ethylene copolymer obtained were as shown in Table 2.
Comparative example 12
An ethylene copolymer was prepared in the same manner as in example 4 except that the metal compound 2 was replaced with the comparative metal compound 2, and the results of the property parameter tests of the ethylene copolymer obtained were as shown in Table 2.
Comparative example 13
An ethylene copolymer was prepared in the same manner as in example 9 except that the metal compound 4 was replaced with the comparative metal compound 4, and the results of the property parameter tests of the ethylene copolymer obtained were as shown in Table 2.
TABLE 1
Table 2 shows the property parameters of the ethylene copolymers prepared in examples 1 to 12 and comparative examples 1 to 13.
The results of Table 2 confirm that the process according to the present invention can produce an ethylene copolymer having a higher content of conjugated diene structural units with a higher catalytic activity, and that the polymer main chain of the produced ethylene copolymer is free or substantially free of unsaturated bonds, while the molecular weight distribution of the produced ethylene copolymer is narrow.
It can also be seen from the results of tables 1 and 2 that when the metal compounds 1 to 4 are used in combination with aluminoxane, the ethylene copolymer prepared not only has an increased molecular weight and a narrow molecular weight distribution index, but also has an increased content of conjugated diene structural units.
Test examples 1 to 2
The ethylene copolymers prepared in examples 3 and 6 were blended on a roll mill with carbon black, peroxide and a vulcanization aid according to the formulations shown in Table 3, respectively. The vulcanization characteristics of the blend were tested at 160 ℃ using an MDR vulcanizer available from alpha technologies for evaluation of the vulcanization rate for 20 minutes. The test results are listed in table 4.
Testing of comparative examples 1-2
The ethylene copolymers prepared in comparative examples 3 and 6 were respectively tested for vulcanization characteristics in the same manner as in test examples 1-2, and the test results are shown in Table 4.
TABLE 3
TABLE 4
| Numbering | Test example 1 | Comparative test example 1 | Test example 2 | Comparative test example 2 |
| tc10(min) | 0.5 | 1.1 | 0.7 | 0.9 |
| tc90(min) | 8.5 | 13.2 | 8.6 | 12.1 |
| MH(dNm) | 92.3 | 45.1 | 90.5 | 56.8 |
| ML(dNm) | 0.5 | 0.6 | 0.5 | 0.7 |
As can be seen from the results of the vulcanization characteristics test in Table 4, the ethylene copolymers prepared in examples 3 and 6 undergo a faster torque rise upon vulcanization, a faster vulcanization rate and a higher degree of vulcanization.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (17)
1. An ethylene polymerization process comprising contacting ethylene with a conjugated diene in the presence of a polymerization catalyst comprising component A and component B,
the component A is selected from metal compounds shown in a formula 1,
in formula 1, M is a metal atom selected from groups IB, IIIB, IVB, VB, VIB, VIIB and VIII,
X1and X2Identical or different, each independently a halogen atom,
rb is a divalent group of a group IIIA element, a divalent group of a group IVA element, a divalent group of a group VA element or a divalent group of a group VIA element,
L1and L2The same or different, each independently selected from the group represented by formula 2 to formula 8, and L1And L2Is not the formula 6, the formula 7 or the formula 8 at the same time,
R1、R2、R3、R4、R5、R6、R7、R8and R9The same or different, each independently is a hydrogen atom, C1-C20Alkyl or C6-C20Aryl of (a);
the component B is an organic aluminum compound and/or an organic boron compound.
2. The method of claim 1, wherein R1、R2、R3、R4、R5、R6、R7、R8And R9Each independently is a hydrogen atom, C1-C10Alkyl or C6-C20Preferably each independently is a hydrogen atom, C1-C5Alkyl or C6-C20More preferably, each of the aryl groups of (a) is independently a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a phenyl group, an anthryl group or a phenanthryl group.
3. The method according to claim 1, wherein in formula 2, R1、R2、R3、R4And R5Are all hydrogen atoms.
4. The method according to claim 1, wherein in formula 3, R2And R4Identical or different, each independently is C1-C20Preferably each independently is C1-C10More preferably each independently is C1-C5Further preferably each independently is C1-C4More preferably each independently of the other is a hydrogen atom, methyl, ethyl, n-propyl or isopropyl, R1、R3And R5Is a hydrogen atom.
5. The method according to claim 1, wherein in formula 4, R1And R4Is C1-C20Is preferably C1-C10More preferably C1-C5Further preferably methyl, ethyl, n-propyl or isopropyl, R2Is C6-C20The aryl group of (a) is,preferably C6-C15More preferably phenyl, anthryl or phenanthryl, R3Is hydrogen.
6. The method of any one of claims 1-5, wherein L1And L2Each independently selected from the group represented by formula 2 to formula 5;
preferably, L1And L2Are the same group.
7. The process according to any one of claims 1 to 6, wherein in formula 1, M is a group IVB metal atom, preferably a zirconium atom; and/or
In formula 1, X1And X2Is a chlorine atom.
8. The method according to any one of claims 1 to 7, wherein Rb in formula 1 is a divalent group of a group IVA element, preferably a divalent group represented by formula 14,
in the formula 14, R1And R2Identical or different, each independently of the others, is C1-C10Is preferably C1-C6More preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.
9. The method according to claim 1, wherein the component A is selected from metal compounds represented by formula 9 to formula 13,
10. the process according to any one of claims 1 to 9, wherein the organoaluminum compound is an aluminoxane and/or a compound represented by formula 15,
in the formula 15, R3、R4And R5Are the same or different and are each independently selected from C1-C10Alkyl of (C)1-C10Alkoxy group of (C)6-C20Aryl of (C)7-C15Alkylaryl of, C7-C15Aralkyl and hydrogen atom of (2), and R3、R4And R5Not being hydrogen atoms at the same time;
preferably, the organoaluminum compound is methylaluminoxane and/or triisobutylaluminum.
11. A process as claimed in any one of claims 1 to 10 wherein the organoboron compound is an organoborate, preferably trityl-tetrakis (pentafluorophenyl) borate.
12. The method of any one of claims 1-11, wherein the molar ratio of component a to component B is 1: 0.1-5000;
preferably, the component B is an organic aluminum compound and an organic boron compound, and the molar ratio of the organic aluminum compound to the organic boron compound is 0.1-1000: 1.
13. the process of any one of claims 1-12, wherein the conjugated diene is butadiene and/or isoprene.
14. The process of any one of claims 1-13, wherein the contacting is carried out at a temperature of-50 ℃ to 150 ℃, the ethylene pressure being 0-100MPa, the pressure being in gauge.
15. The process according to any one of claims 1 to 14, wherein said component a is used in an amount ranging from 0.1 to 100 μmol with respect to 1mol of conjugated diene.
16. The process according to any one of claims 1 to 15, wherein the contacting is carried out in the presence of a molecular weight regulator, and the number average molecular weight of the ethylene copolymer is 10,000 or more, preferably 12,000 to 500,000, more preferably 14,000 to 400,000, further preferably 16,000 to 350,000, still further preferably 20,000 to 320,000.
17. An ethylene copolymer prepared by the process of any one of claims 1-16.
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| KR1020237020824A KR20230109729A (en) | 2020-11-20 | 2020-11-27 | Ethylene copolymers, methods for their preparation, compositions, cross-linked polymers and tires |
| US18/253,626 US20240010768A1 (en) | 2020-11-20 | 2020-11-27 | Ethylene copolymer and method for preparation thereof and composition and crosslinked polymer and tire |
| EP20962168.9A EP4242239A1 (en) | 2020-11-20 | 2020-11-27 | Ethylene copolymer and method for preparation thereof and composition and crosslinked polymer and tire |
| PCT/CN2020/132147 WO2022104877A1 (en) | 2020-11-20 | 2020-11-27 | Ethylene copolymer and method for preparation thereof and composition and crosslinked polymer and tire |
| JP2023530770A JP2023549958A (en) | 2020-11-20 | 2020-11-27 | Ethylene copolymer and its production method, composition, crosslinked polymer and tire |
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| US5191052A (en) * | 1985-06-21 | 1993-03-02 | Exxon Chemical Patents Inc. | Copolymers of ethylene and 1,3-butadiene |
| US20030036610A1 (en) * | 1999-12-28 | 2003-02-20 | Ofelia Fusco | Process for the preparation of ethylene polymers |
| CN102356100A (en) * | 2009-03-30 | 2012-02-15 | 三井化学株式会社 | Copolymer of olefin and conjugated diene, and process for producing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5191052A (en) * | 1985-06-21 | 1993-03-02 | Exxon Chemical Patents Inc. | Copolymers of ethylene and 1,3-butadiene |
| US20030036610A1 (en) * | 1999-12-28 | 2003-02-20 | Ofelia Fusco | Process for the preparation of ethylene polymers |
| CN102356100A (en) * | 2009-03-30 | 2012-02-15 | 三井化学株式会社 | Copolymer of olefin and conjugated diene, and process for producing same |
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| WO2023226318A1 (en) * | 2022-05-27 | 2023-11-30 | 中国石油化工股份有限公司 | Metallocene complex and preparation method therefor, catalyst composition, olefin polymerization method and olefin polymer |
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