CN115260367A - Application of rare earth metal complex in preparation process of ethylene/butadiene copolymer from ethylene and 1, 3-butadiene - Google Patents
Application of rare earth metal complex in preparation process of ethylene/butadiene copolymer from ethylene and 1, 3-butadiene Download PDFInfo
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- CN115260367A CN115260367A CN202211037070.5A CN202211037070A CN115260367A CN 115260367 A CN115260367 A CN 115260367A CN 202211037070 A CN202211037070 A CN 202211037070A CN 115260367 A CN115260367 A CN 115260367A
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Abstract
The invention provides the application of rare earth metal complexes in the process of preparing ethylene/butadiene copolymer from ethylene and 1, 3-butadiene; the rare earth metal complex has a general formula shown in a formula (I). The invention takes the ethylene/butadiene copolymer prepared by the rare earth metal complex as a catalyst, and further obtains the ethylene/butadiene copolymer with specific composition and structure and high breakdown voltage. The breakdown field strength of the binary copolymer is 260-370 mm/KV, the content of butadiene structural units in the copolymer is not less than 65mol%, the content of reverse 1, 4-structures in the butadiene structural units is not less than 10mol%, and more importantly, the melting point of crystalline sequences in the copolymer is 100-140 ℃.
Description
Technical Field
The invention belongs to the technical field of ethylene/butadiene copolymer materials, and relates to application of a rare earth metal complex in the process of preparing an ethylene/butadiene copolymer from ethylene and 1, 3-butadiene, a preparation method of the ethylene/butadiene copolymer, in particular to application of the rare earth metal complex in the process of preparing the ethylene/butadiene copolymer from ethylene and 1, 3-butadiene, and a preparation method of the ethylene/butadiene copolymer with high breakdown voltage.
Background
China has become the second largest ethylene producing country in the world after the United states, and the shale gas revolution provides a large amount of cheap ethane as an ethylene cracking raw material for the ethylene industry, which causes serious impact on the traditional ethylene industry which uses naphtha as the cracking raw material in China. Meanwhile, the polyethylene industry, which is a major downstream industry of the ethylene industry, faces a dilemma that although the yield increases year by year, the profitability decreases, and therefore, it is important to increase the competitiveness of the ethylene industry by increasing the added value of ethylene.
Ethylene and butadiene are copolymerized, and with the change of the feeding proportion of the two monomers, a series of materials with different performances such as novel rubber reinforced by plastics, plastics containing unsaturated double bond functional groups and the like can be theoretically prepared. Ethylene homopolymer is a plastic and cis-polybutadiene is a rubber. The polyethylene molecular chain has the advantages of high flexibility, strong crystallization capacity, high modulus and strength, good toughness and tear resistance; the butadiene rubber molecular chain is extremely flexible, excellent in elasticity and cold resistance, but low in tensile and tear strength. The polyethylene sequence is introduced into the rubber, so that the double bond content in the rubber is reduced, the ageing resistance and ultraviolet resistance of the rubber are improved, the rubber can be enhanced, and the application field of the rubber is widened. Unsaturated carbon-carbon double bonds are introduced into the polyolefin chains to serve as reactive functional groups, so that the preparation of high-performance and functional polyolefin through chemical conversion is facilitated. Therefore, ethylene/conjugated diene copolymerization has attracted research interest since the invention of Ziegler-Natta catalysts.
The crosslinked polyethylene has good electrical properties, high insulation resistance, low dielectric loss tangent and high breakdown field strength (usually, the breakdown field strength is about 260 mm/KV). And the material has a three-dimensional reticular macromolecular structure, good mechanical property and environmental stress cracking resistance, and the long-term working temperature of the material can reach 90 ℃. At present, the crosslinked polyethylene is mainly prepared into the special crosslinked polyethylene for the cable insulating material by low-density polyethylene through methods such as chemical crosslinking, silane crosslinking, irradiation crosslinking, ultraviolet crosslinking and the like. Low density polyethylene is generally prepared from ethylene by radical polymerization under high pressure, and its heat resistance is not high, but in practice, the application of crosslinked polyethylene in power transmission is limited by the fact that the cable generates heat highly as the distance of power transmission increases.
In contrast, in the patent documents which have been disclosed in the prior art, rubbers are produced by ethylene/butadiene copolymerization, and therefore the copolymers produced do not have an excessively high ethylene content and do not contain crystalline polyethylene sequences or only contain polyethylene segments of short sequence length. Therefore, materials with high breakdown field strength have not been prepared by ethylene-butadiene copolymerization before.
Therefore, how to further improve the performance of the ethylene/butadiene copolymer, and solve the above limitations of the current application of the ethylene/butadiene copolymer, makes it a promising class of low dielectric constant materials, and has become one of the focuses of much attention of many researchers in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an application of a rare earth metal complex in the process of preparing an ethylene/butadiene copolymer from ethylene and 1, 3-butadiene, a preparation method of the ethylene/butadiene copolymer, and particularly to a preparation method of an ethylene/butadiene copolymer with high breakdown voltage. The invention adopts the specific rare earth metal complex for preparing the ethylene/butadiene copolymer, can obtain the copolymer material with low dielectric constant through crosslinking, and has higher breakdown voltage.
The invention provides the application of rare earth metal complexes in the process of preparing ethylene/butadiene copolymer from ethylene and 1, 3-butadiene;
the rare earth metal complex has a general formula shown in a structure of formula (I):
wherein M is one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;
R 1 、R 2 and R 3 Each independently selected from a hydrogen atom, an alkyl or haloalkyl group having 1 to 10 carbon atoms, an alkenyl or haloalkenyl group having 2 to 20 carbon atoms, an aralkyl or haloaralkyl group having 6 to 20 carbon atoms, a silyl group having 1 to 14 carbon atoms;
X 1 and X 2 Each independently selected from hydrogen, linear or branched aliphatic or cycloaliphatic radicals containing from 1 to 20 carbon atoms, phenyl substituted by linear or branched alkyl or cyclic aliphatic or aromatic radicals containing from 1 to 20 carbon atoms, linear or branched alkoxy radicals containing from 1 to 20 carbon atoms, linear or branched alkylamino radicals containing from 1 to 20 carbon atoms, linear or branched arylamino radicals containing from 1 to 20 carbon atoms, linear or branched silyl radicals containing from 1 to 20 carbon atoms, borohydride radicals, allyl and allyl derivatives, halogens;
l is selected from one of tetrahydrofuran, glycol dimethyl ether and pyridine;
w is an integer of 0 to 3.
Preferably, the ethylene/butadiene copolymer consists of ethylene structural units and butadiene structural units;
wherein, the content of the ethylene structural unit is not less than 65mol percent, and the content of the trans-1, 4-structural unit in the butadiene structural unit is not less than 10mol percent;
the number average molecular weight of the copolymer is 10000-500000;
the ethylene/butadiene copolymer is an ethylene/butadiene copolymer containing a crystalline sequence.
Preferably, the melting point of the crystalline sequence in the copolymer is 100-140 ℃;
the content of ethylene structural units in the copolymer is not less than 75mol%;
the content of trans-1, 4-structural units in butadiene structural units in the copolymer is not less than 20mol%;
the molecular weight distribution of the copolymer is not higher than 8;
the copolymer is a binary copolymer.
Preferably, the melting point of the crystalline sequence in the copolymer is 105-135 ℃;
the ethylene/butadiene copolymer has a high breakdown voltage;
the breakdown field strength of the ethylene/butadiene copolymer is 260-370 mm/KV.
Preferably, the use is in particular as a catalyst in a catalyst system;
the catalyst system further comprises an organoborate compound and an organoaluminum compound;
the ethylene/butadiene copolymer is prepared from ethylene and 1, 3-butadiene in a reaction medium under the action of a catalytic system;
the copolymer includes an ethylene/butadiene copolymer for a rubber material.
The invention provides a preparation method of an ethylene/butadiene copolymer, which comprises the following steps:
1) Initiating polymerization reaction of ethylene, 1, 3-butadiene and a catalyst system in a reaction medium to obtain an ethylene/butadiene binary copolymer;
the catalyst system comprises an organic boron salt compound, an organic aluminum compound and a rare earth metal complex;
the rare earth metal complex has a general formula shown in a structure of formula (I):
wherein M is one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;
R 1 、R 2 and R 3 Each independently selected from the group consisting of a hydrogen atom, an alkyl or haloalkyl group having 1 to 10 carbon atoms, an alkenyl or haloalkenyl group having 2 to 20 carbon atoms, an aralkyl or haloaralkyl group having 6 to 20 carbon atoms, a silyl group having 1 to 14 carbon atoms;
X 1 and X 2 Each independently selected from hydrogen, straight or branched aliphatic or cycloaliphatic radicals having from 1 to 20 carbon atoms, phenyl, radicals having from 1 to 20 carbon atomsPhenyl substituted by linear or branched alkyl or cyclic aliphatic group or aromatic group, linear or branched alkoxy containing 1 to 20 carbon atoms, linear or branched alkylamino containing 1 to 20 carbon atoms, linear or branched arylamine containing 1 to 20 carbon atoms, linear or branched silane group containing 1 to 20 carbon atoms, borohydride group, allyl and allyl derivatives, halogen;
l is one selected from tetrahydrofuran, glycol dimethyl ether and pyridine;
w is an integer of 0 to 3.
Preferably, the organoboron salt compound comprises an ionic compound formed from organoboron anions and cations, and/or an organoboron compound;
the organoboron anion includes tetraphenyl borate, tetrakis (mono-fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate ([ B (C) 6 F 5 ) 4 ] - ) Tetra (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [ tris (pentafluorophenyl), phenyl]One or more of borate and undecahydrido-7, 8-dicarbaundecaborate;
the cation comprises a carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptatrienyl cation, or ferrocenium cation containing a transition metal;
the organoboron compound includes B (C) 6 F 5 ) 3 ；
The organoaluminum compound comprises one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, and ethyldi (p-tolyl) aluminum;
the organoboron salt compound is specifically an organoboron salt compound solution.
Preferably, the molar ratio of the organic boron salt compound to the rare earth metal complex is (1-10): (10-1);
the molar ratio of the organic aluminum compound to the rare earth metal complex is (2-300): 1;
the pressure of the ethylene is 1 to 50 atmospheric pressures.
Preferably, the reaction medium comprises one or more of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides and cycloalkanes;
the concentration of said 1, 3-butadiene in the reaction medium is lower than 2mol/L;
the temperature of the polymerization reaction is-20 to 150 ℃.
Preferably, the step 1) specifically comprises:
11 Mixing 1, 3-butadiene, a part of the organoaluminum compound solution and a reaction medium, and introducing ethylene to obtain a polymerization reaction system;
12 Mixing the rare earth metal complex solution, the other part of the organic aluminum compound, the organic boron salt compound and the reaction medium again to obtain a catalyst solution, heating the catalyst solution in the polymerization reaction system obtained in the previous step, increasing the pressure of ethylene, and carrying out polymerization reaction to obtain the ethylene/butadiene binary copolymer.
The invention provides the application of rare earth metal complexes in the process of preparing ethylene/butadiene copolymer from ethylene and 1, 3-butadiene; the rare earth metal complex has a general formula shown in a formula (I). Compared with the prior art, the invention aims at the defects of the existing ethylene/butadiene copolymer in performance, especially the defect of difficult application in the high breakdown field strength environment. The invention creatively uses the ethylene/butadiene copolymer prepared by using the rare earth metal complex with a specific structure and composition as a catalyst, and further obtains the ethylene/butadiene copolymer with a high breakdown voltage and a specific composition and structure. The breakdown field strength of the binary copolymer is 260-370 mm/KV, the content of ethylene structural units in the copolymer is not less than 65mol%, the content of reverse 1, 4-structures in butadiene structural units is not less than 10mol%, and more importantly, the melting point of crystalline sequences in the copolymer is 100-140 ℃. The binary copolymer of ethylene and 1, 3-butadiene prepared by the invention is a random copolymer or a multi-block copolymer containing 1, 3-butadiene monomer units and ethylene monomer units, has high content of ethylene, and has crystalline polyethylene segments with longer sequence length. The copolymer can obtain a material with low dielectric constant through crosslinking, has higher breakdown voltage, and is a novel plastic material which is not reported in the prior art such as patents, documents and the like.
The invention also provides a preparation method of the copolymer, and particularly relates to a catalyst system consisting of an amidino rare earth metal complex with a specific structure, an organic boron compound and alkyl aluminum, so that ethylene and butadiene monomers are copolymerized to obtain the ethylene/butadiene copolymer. The invention adopts two monomers of ethylene and 1, 3-butadiene with great difference in polymerization reaction mechanism and polymerization activity, and can obtain high catalytic activity to the ethylene and 1, 3-butadiene monomers by adjusting the catalyst structure and changing the polymerization reaction process.
The ethylene-butadiene provided by the invention has lower dielectric constant, can be used in an environment with higher breakdown field strength, is a low dielectric constant material with a great development prospect, solves the application limitation of the existing ethylene-butadiene copolymer, and greatly widens the application depth and breadth.
Experimental results show that the breakdown voltage of the ethylene/butadiene copolymer provided by the invention can reach 370mm/KV at most.
Drawings
FIG. 1 is a representation of a copolymer sample prepared according to example 1 of the present invention 1 H NMR spectrum;
FIG. 2 shows a sample of a copolymer prepared in example 6 of the present invention 1 H NMR spectrum;
FIG. 3 is a sample of the copolymer prepared in example 6 of the present invention 13 C NMR spectrogram;
FIG. 4 is a graph of the mechanical properties of a sample of the copolymer prepared in example 7 of the present invention;
FIG. 5 is a graph showing mechanical properties of a sample of the copolymer prepared in example 8 of the present invention;
FIG. 6 is a plot of the breakdown voltage measurements for samples of copolymers prepared in example 9 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All of the starting materials of the present invention are not particularly limited in their purity, and the present invention preferably employs purity requirements that are conventional in the art of analytically pure or ethylene/butadiene copolymer preparation.
The expression of the substituent in the present invention is not particularly limited, and any expression known to those skilled in the art can be used, and the meaning of the substituent can be correctly understood by those skilled in the art based on the general knowledge of the expression.
All the raw materials of the invention, the marks or the abbreviations thereof belong to the conventional marks or the abbreviations thereof in the field, each mark and the abbreviation thereof are clear and definite in the field of related applications, and the technical personnel in the field can purchase the raw materials from the market or prepare the raw materials by the conventional method according to the marks, the abbreviations and the corresponding applications.
The invention provides the application of rare earth metal complexes in the process of preparing ethylene/butadiene copolymer from ethylene and 1, 3-butadiene;
the rare earth metal complex has a general formula shown in a structure of formula (I):
wherein M is one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;
R 1 、R 2 and R 3 Each independently selected from hydrogen atoms, alkyl or haloalkyl groups having 1 to 10 carbon atoms, and 2 to 20 carbonsAn alkenyl or haloalkenyl group, an aralkyl or haloaralkyl group having 6 to 20 carbon atoms, a silyl group having 1 to 14 carbon atoms;
X 1 and X 2 Each independently selected from hydrogen, linear or branched aliphatic or alicyclic group containing 1 to 20 carbon atoms, phenyl, linear or branched alkyl group containing 1 to 20 carbon atoms, or phenyl substituted by cyclic aliphatic or aromatic group, linear or branched alkoxy group containing 1 to 20 carbon atoms, linear or branched alkylamino group containing 1 to 20 carbon atoms, linear or branched arylamine group containing 1 to 20 carbon atoms, linear or branched silyl group containing 1 to 20 carbon atoms, borohydride group, allyl group and allyl group derivatives, halogen;
l is selected from one of tetrahydrofuran, glycol dimethyl ether and pyridine;
w is an integer of 0 to 3.
In the present invention, the copolymer is preferably composed of an ethylene structural unit and a butadiene structural unit, wherein the content of the ethylene structural unit is preferably not less than 65mol%, and the content of the trans 1, 4-structural unit in the butadiene structural unit is preferably not less than 10mol%.
In the present invention, the content of the ethylene structural unit in the copolymer is preferably not less than 65mol%, more preferably not less than 70mol%, still more preferably not less than 75mol%. Specifically, the main chain of the copolymer preferably contains ethylene units, and the content of the ethylene units is preferably more than 65mol% of the whole copolymer, more preferably more than 68mol% of the whole copolymer, most preferably 65 to 93mol%, more preferably 68 to 91mol%, more preferably 70 to 89mol%, more preferably 72 to 87mol%, more preferably 74 to 85mol%, most preferably 80mol% of the whole copolymer.
In the present invention, the content of the trans 1, 4-structural unit in the butadiene structural unit in the copolymer is preferably not less than 10mol%, more preferably not less than 20mol%, still more preferably not less than 30mol%.
In the present invention, the content of the trans 1, 4-structural unit in the ethylene structural unit + the butadiene structural unit is 100mol% or less.
In the present invention, the copolymer is preferably a binary copolymer.
In the present invention, the ethylene/butadiene copolymer is preferably an ethylene/butadiene copolymer having a crystalline sequence.
In the present invention, the melting point of the crystalline sequence in the copolymer is preferably 100 to 140 ℃, may be 105 to 135 ℃, preferably 110 to 130 ℃, and more preferably 115 to 125 ℃.
The ethylene/butadiene copolymer preferably has a high breakdown voltage;
in the invention, the breakdown field strength of the ethylene/butadiene copolymer is 260-370 mm/KV, can be 280-350 mm/KV, and is preferably 300-330 mm/KV.
In the present invention, the bipolymer backbone comprises ethylene units and 1, 3-butadiene units; the content of the 1, 3-butadiene structural unit is 5-35 mol%; the content of the ethylene structural unit is 65-95 mol%.
The content of the 1, 3-butadiene unit is preferably more than 5mol% and less than 35mol% of the whole binary copolymer, more preferably more than 8mol% and less than 32mol% of the whole binary copolymer, and most preferably more than 10mol% and less than 30mol% of the whole binary copolymer.
Wherein the content of 1,4 butadiene structural units in the copolymer is preferably higher than 75mol%.
Wherein the content of trans 1,4 butadiene structural units in the copolymer is preferably higher than 20mol%.
The main chain of the copolymer preferably further contains an ethylene unit, and the content of the ethylene unit is preferably more than 65mol%, more preferably more than 68mol%, most preferably 70 to 93mol%, more preferably 72 to 91mol%, more preferably 70 to 89mol%, more preferably 72 to 87mol%, more preferably 74 to 85mol%, more preferably 80mol% of the entire copolymer.
In the present invention, the ethylene/butadiene copolymer is preferably an ethylene/butadiene copolymer having a crystalline sequence.
In the present invention, the copolymer is preferably prepared from ethylene and 1, 3-butadiene under the action of a catalytic system.
In the present invention, the molecular weight distribution of the copolymer is preferably not higher than 8, more preferably not higher than 6, and still more preferably not higher than 4. Specifically, the range may be 1 to 8, more preferably 1 to 5, and most preferably 1 to 3.
In the present invention, the number average molecular weight of the copolymer is preferably 10000 to 500000, more preferably 100000 to 400000, and still more preferably 200000 to 300000.
In the present invention, the rare earth metal complex preferably has a general formula shown in the structure of formula (I):
in the present invention, M is preferably one selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
In the present invention, R 1 、R 2 And R 3 Each independently is preferably selected from a hydrogen atom, an alkyl or haloalkyl group having 1 to 10 carbon atoms, an alkenyl or haloalkenyl group having 2 to 20 carbon atoms, an aralkyl or haloalkaralkyl group having 6 to 20 carbon atoms, a silyl group having 1 to 14 carbon atoms, more preferably from a hydrogen atom, an alkyl or haloalkyl group having 3 to 8 carbon atoms, an alkenyl or haloalkenyl group having 6 to 16 carbon atoms, an aralkyl or haloalkaralkyl group having 9 to 17 carbon atoms, a silyl group having 4 to 10 carbon atoms, more preferably from a hydrogen atom, an alkyl or haloalkyl group having 5 to 6 carbon atoms, an alkenyl or haloalkenyl group having 10 to 12 carbon atoms, an aralkyl or haloalkaralkyl group having 11 to 14 carbon atoms, a silyl group having 6 to 8 carbon atoms.
In the present invention, X 1 And X 2 Each independently preferably selected from hydrogen, straight or branched aliphatic or cycloaliphatic radicals having from 1 to 20 carbon atoms, phenyl, straight or branched aliphatic or cycloaliphatic radicals having from 1 to 20 carbon atomsPhenyl substituted with a branched or cyclic aliphatic or aromatic group, a linear or branched alkoxy group having 1 to 20 carbon atoms, a linear or branched alkylamino group having 1 to 20 carbon atoms, a linear or branched arylamine group having 1 to 20 carbon atoms, a linear or branched silyl group having 1 to 20 carbon atoms, a borohydride group, an allyl group and an allyl derivative, a halogen, more preferably selected from hydrogen, a linear or branched aliphatic or alicyclic group having 5 to 16 carbon atoms, phenyl, a linear or branched alkyl group having 5 to 16 carbon atoms or a phenyl substituted with a cyclic aliphatic or aromatic group, a linear or branched alkoxy group having 5 to 16 carbon atoms, a linear or branched alkylamino group having 5 to 16 carbon atoms, a linear or branched arylamine group having 5 to 16 carbon atoms, a linear or branched silyl group having 5 to 16 carbon atoms, a borohydride group, an allyl and allyl derivative, a halogen, more preferably selected from hydrogen, a linear or branched aliphatic or alicyclic group having 5 to 16 carbon atoms, a phenyl, a linear or branched aliphatic or aliphatic group having 9 to 12 carbon atoms or a linear or branched alkyl group having 9 to 12 carbon atoms, a linear or branched alkoxy group having 9 to 12 carbon atoms, a halogen, and a linear or branched arylamine group.
In the present invention, L is selected from one of tetrahydrofuran, ethylene glycol dimethyl ether and pyridine.
In the present invention, w is preferably an integer of 0 to 3, more preferably 0, 1, 2 or 3.
In the present invention, the use is particularly preferably the use as a catalyst in a catalyst system.
In the present invention, the catalyst system further comprises an organoborate compound and an organoaluminum compound.
In the present invention, the ethylene/butadiene copolymer is preferably prepared from ethylene and 1, 3-butadiene in a reaction medium, under the action of a catalytic system.
In the present invention, the copolymer preferably includes an ethylene/butadiene copolymer for a rubber material.
The invention is a complete and refined integral technical scheme, better ensures the structure of the ethylene/butadiene copolymer, further improves the breakdown voltage of the ethylene/butadiene copolymer, and the ethylene/butadiene copolymer in the application preferably has the following structure:
an ethylene/butadiene copolymer having a high breakdown voltage, said copolymer being composed of ethylene structural units and butadiene structural units, wherein the content of ethylene structural units is not less than 65mol%, the content of trans 1, 4-structural units in butadiene structural units is not less than 10mol%, and the melting point of crystalline sequences in the copolymer is between 100 and 140 ℃.
Specifically, the breakdown field strength of the copolymer is 260-370 mm/KV.
Specifically, the content of the ethylene structural unit in the copolymer is not less than 75mol%.
Specifically, the main chain of the binary copolymer comprises ethylene units and 1, 3-butadiene units; the content of the 1, 3-butadiene structural unit is 5-35 mol%; the content of the ethylene structural unit is 65-95 mol%.
Specifically, the content of trans 1, 4-structural units in butadiene structural units in the copolymer is not less than 20mol%.
Specifically, the melting point of the crystalline sequence in the copolymer is 105-135 ℃.
In particular, the molecular weight of the copolymer is between 10000 and 500000.
Specifically, the molecular weight distribution of the copolymer is not higher than 8.
Further, the present invention provides a binary copolymer with high breakdown field strength, wherein the monomers for preparing the binary copolymer comprise: ethylene and 1, 3-butadiene, the binary copolymer being a random copolymer or a multiblock copolymer;
specifically, the main chain of the binary copolymer comprises ethylene units and 1, 3-butadiene units; the content of the 1, 3-butadiene structural unit is 5-35 mol%; the content of the ethylene structural unit is 65-95 mol%.
Specifically, the content of the 1, 3-butadiene unit is preferably more than 5mol% and less than 35mol% of the whole binary copolymer, more preferably more than 8mol% and less than 32mol% of the whole binary copolymer, and most preferably more than 10mol% and less than 30mol% of the whole binary copolymer.
Specifically, the content of 1,4 butadiene structural units in the copolymer is preferably more than 75mol%.
In particular, the content of trans 1,4 butadiene structural units in the copolymer is preferably higher than 20mol%.
Specifically, the main chain of the copolymer preferably further contains ethylene units, and the content of the ethylene units is preferably more than 65mol%, more preferably more than 68mol%, most preferably 70 to 93mol%, more preferably 72 to 91mol%, more preferably 70 to 89mol%, more preferably 72 to 87mol%, more preferably 74 to 85mol%, most preferably 80mol% of the whole copolymer.
In particular, the crystalline sequences in the copolymer have a melting point between 105 ℃ and 135 ℃, more preferably between 110 ℃ and 130 ℃, more preferably between 115 ℃ and 125 ℃, and most preferably 125 ℃.
Specifically, the number average molecular weight of the binary copolymer is preferably 10000 to 500000, more preferably 50000 to 400000, and still more preferably 100000 to 400000; the molecular weight distribution of the bipolymer is preferably between 1 and 8, more preferably between 1 and 5, and most preferably between 1 and 3.
The invention also provides a preparation method of the ethylene/butadiene copolymer, which comprises the following steps:
1) Initiating polymerization reaction of ethylene, 1, 3-butadiene and a catalyst system in a reaction medium to obtain an ethylene/butadiene binary copolymer;
the catalyst system comprises an organic boron salt compound, an organic aluminum compound and a rare earth metal complex;
the rare earth metal complex has a general formula shown in a structure of formula (I):
wherein M is one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;
R 1 、R 2 and R 3 Each independently selected from a hydrogen atom, an alkyl or haloalkyl group having 1 to 10 carbon atoms, an alkenyl or haloalkenyl group having 2 to 20 carbon atoms, an aralkyl or haloaralkyl group having 6 to 20 carbon atoms, a silyl group having 1 to 14 carbon atoms;
X 1 and X 2 Each independently selected from hydrogen, linear or branched aliphatic or cycloaliphatic radicals containing from 1 to 20 carbon atoms, phenyl substituted by linear or branched alkyl or cyclic aliphatic or aromatic radicals containing from 1 to 20 carbon atoms, linear or branched alkoxy radicals containing from 1 to 20 carbon atoms, linear or branched alkylamino radicals containing from 1 to 20 carbon atoms, linear or branched arylamino radicals containing from 1 to 20 carbon atoms, linear or branched silyl radicals containing from 1 to 20 carbon atoms, borohydride radicals, allyl and allyl derivatives, halogens;
l is selected from one of tetrahydrofuran, glycol dimethyl ether and pyridine;
w is an integer of 0 to 3.
In the present invention, the structure, the substituent group and the corresponding preferred principle of the rare earth metal complex in the preparation method may preferably correspond to the structure, the substituent group and the corresponding preferred principle of the rare earth metal complex in the ethylene/butadiene copolymer one by one, and are not described in detail herein.
In the present invention, the organoboron salt compound preferably includes an ionic compound formed from an organoboron anion and a cation, and/or an organoboron compound, more preferably includes an ionic compound formed from an organoboron anion and a cation, or an organoboron compound.
In the present invention, the organoboron anion preferably includes one or more of 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 undecahydrido-7, 8-dicarbaundecaborate, more preferably tetraphenyl borate, tetrakis (mono-fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetrakis (tolyl) borate, tetrakis (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [ tris (pentafluorophenyl), phenyl ] borate or hydrido-7, 8-dicarbaundecaborate.
In the present invention, the cation preferably includes a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation or a ferrocenium cation containing a transition metal.
In the present invention, the organoboron compound preferably comprises B (C6F 5) 3 。
In the present invention, the organoaluminum compound preferably includes one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, and ethyldi (p-tolyl) aluminum, and more preferably trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, or ethyldi (p-tolyl) aluminum.
In the present invention, the organoboron salt compound is particularly preferably an organoboron salt compound solution.
In the present invention, the molar ratio of the organoboron salt compound to the rare earth metal complex is preferably (1 to 10): (10-1), more preferably (3-8): (10-1), more preferably (5-6): (10-1), more preferably (1-10): (8 to 3), more preferably (1 to 10): (6-5).
In the present invention, the molar ratio of the organoaluminum compound to the rare earth metal complex is preferably (2 to 300): 1, more preferably (20 to 200): 1, more preferably (50 to 100): 1.
in the present invention, the pressure of ethylene is preferably 1 to 50 atmospheres, more preferably 10 to 40 atmospheres, and still more preferably 20 to 30 atmospheres.
In the present invention, the reaction medium preferably comprises one or more of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides and cycloalkanes, more preferably aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides or cycloalkanes.
In the present invention, the concentration of said 1, 3-butadiene in the reaction medium is preferably lower than 2mol/L, more preferably lower than 1.5mol/L, more preferably lower than 1.2mol/L.
In the present invention, the temperature of the polymerization reaction is preferably-20 to 150 ℃, more preferably 0 to 100 ℃, and still more preferably 20 to 50 ℃.
In the present invention, the step 1) is particularly preferably:
1) Mixing 1, 3-butadiene, a part of organic aluminum compound solution and a reaction medium, and introducing ethylene to obtain a polymerization reaction system;
2) And (2) mixing the rare earth metal complex solution, the other part of the organic aluminum compound, the organic boron salt compound and the reaction medium again to obtain a catalyst solution, heating the catalyst solution in the polymerization reaction system obtained in the step (a), increasing the pressure of ethylene, and carrying out polymerization reaction to obtain the ethylene/butadiene binary copolymer.
The invention is a complete and detailed integral technical scheme, better ensures the structure of the ethylene/butadiene copolymer, and further improves the breakdown voltage of the ethylene/butadiene copolymer, and the preparation method of the ethylene/butadiene copolymer preferably comprises the following steps:
the preparation method of the binary copolymer comprises the following steps:
initiating polymerization reaction of ethylene and butadiene in a reaction medium under a catalytic system to obtain a binary copolymer;
the catalytic system comprises: an organic boron salt compound, an organic aluminum compound and a rare earth metal complex.
Specifically, the concentration of butadiene in the reaction system is not higher than 2mol/L, and the pressure of ethylene is not higher than 50bar.
Specifically, the reaction medium is selected from one or more of aliphatic saturated hydrocarbon, aromatic hydrocarbon, aryl halide and cyclane.
The rare earth metal complex has the structure of formula I:
m in the formula I is one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;
R 1 、R 2 and R 3 Independently selected from the group consisting of a hydrogen atom, an alkyl or haloalkyl group having 1 to 10 carbon atoms, an alkenyl or haloalkenyl group having 2 to 20 carbon atoms, an aralkyl or haloaralkyl group having 6 to 20 carbon atoms, a silyl group having 1 to 14 carbon atoms;
X 1 and X 2 Being a monoanionic ligand, X 1 And X 2 Independently selected from hydrogen, linear or branched aliphatic or cycloaliphatic radicals containing from 1 to 20 carbon atoms, phenyl substituted by linear or branched alkyl or cyclic aliphatic or aromatic radicals containing from 1 to 20 carbon atoms, linear or branched alkoxy radicals containing from 1 to 20 carbon atoms, linear or branched alkylamino radicals containing from 1 to 20 carbon atoms, linear or branched arylamino radicals containing from 1 to 20 carbon atoms, linear or branched silyl radicals containing from 1 to 20 carbon atoms, borohydride radicals, allyl and allyl derivatives or halogens;
l is a neutral Lewis base selected from one of tetrahydrofuran, glycol dimethyl ether and pyridine;
w is an integer of 0 to 3.
Specifically, the rare earth metal complex is preferably one of formula 1 to formula 8:
the source of the rare earth metal complex is not particularly limited in the present invention, and the rare earth metal complex can be prepared according to a method well known to those skilled in the art, for example, according to a method disclosed in j.am.chem.soc.2004,126,30, 9182-9183.
Specifically, the organoboron compound is preferably an ionic compound formed by an organoboron anion and a cation; the organoboron anion is preferably selected from tetraphenylborate ([ BPh ] 4 ] - ) Tetrakis (pentafluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate ([ B (C) is preferred), and tetrakis (pentafluorophenyl) borate ([ B (C) is preferred 6 F 5 ) 4 ] - ) Tetrakis (tetrafluoromethylphenyl) borate, tetrakis (tolyl) borate, tetrakisxylyl borate, (triphenyl, pentafluorophenyl) borate, [ tris (pentafluorophenyl), phenyl]Borate or undecahydrido-7, 8-dicarbaundecaborate; the cation is preferably selected from the group consisting of a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation or a ferrocenium cation containing a transition metal; the carbonium cation preferably comprises a trisubstituted carbonium cation such as triphenylcarbonium cation ([ Ph) 3 C] + ) And tri (substituted phenyl) carbonium cations, and tri (substituted phenyl) carbonium cations such as tri (tolyl) carbonium cation; the ammonium cation preferably includes trialkylammonium cations such as trimethylammonium cation, triethylammonium cation ([ NEt ] 3 H] + ) Tripropylammonium cation and tributylammonium cation; n, N-dialkylanilinium cations such as N, N-dimethylanilinium cation ([ PhNMe) 2 H] + ) N, N-diethylanilinium and N, N-2,4, 6-pentamethylanilinium; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation; the phosphonium cation preferably comprises a triarylphosphonium cation such as triphenylphosphonium cation, tri (tolyl) phosphonium cation or tri (xylyl) phosphonium cation.
In particular, the organoboron salt compound is preferably selected from [ Ph 3 C][B(C 6 F 5 ) 4 ]、[PhNMe 2 H][BPh 4 ]、[NEt 3 H][BPh 4 ]Or [ PhNMe 2 H][B(C 6 F 5 ) 4 ](ii) a It is also possible to use organoboron compounds having the same function as the organoboron salt compound, such as B (C) 6 F 5 ) 3 。
Specifically, the organoaluminum compound is preferably selected from trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, or ethyldi (p-tolyl) aluminum.
Specifically, the organoaluminum compound is preferably dissolved in a solvent, and the solvent is preferably toluene.
Specifically, the catalytic system preferably further comprises a solvent; the solvent is preferably selected from toluene.
Specifically, the concentration of the 1, 3-butadiene in the polymerization system is preferably less than 2mol/L, more preferably 0.05 to 2mol/L, still more preferably 0.05 to 1.0mol/L, and most preferably 0.1 to 0.8mol/L.
The amount of the catalyst system used in the present invention is not particularly limited, and those skilled in the art can select an appropriate amount of the catalyst system to ensure the polymerization reaction according to the amount of the catalyst for monomer polymerization known in the art.
Specifically, the molar ratio of the organoboron salt compound to the rare earth metal complex is preferably (1 to 10): (10-1), more preferably (2-8): (8-2), most preferably (3-6): (6-3); in embodiments of the present invention, the molar ratio of the organoboron salt compound and the rare earth metal complex is preferably (0.5 to 10): 1, more preferably (1 to 8): 1, more preferably (2 to 6): 1, and most preferably 1.
Specifically, the molar ratio of the organoaluminum compound to the rare earth metal complex is preferably (2 to 300): 1, more preferably (5 to 250): 1, more preferably (5 to 200): 1, more preferably (5 to 150): 1, more preferably (5 to 120): 1, most preferably (5 to 60): 1.
specifically, the polymerization temperature is preferably-20 to 150 ℃, more preferably-10 to 120 ℃, more preferably 10 to 90 ℃, more preferably 20 to 80 ℃, more preferably 30 to 60 ℃, and most preferably 40 to 50 ℃.
Specifically, the pressure of ethylene in the reaction process is preferably 1 to 50 atmospheres, more preferably 1 to 45 atmospheres, and still more preferably 1 to 30 atmospheres.
Specifically, the polymerization reaction time of the present invention is not particularly limited, and is selected according to the amount of the catalyst to be used and the size of the reaction system. Wherein the polymerization reaction is carried out by an intermittent kettle, and the reaction time is 1 minute to 10 hours; if the polymerization reaction is carried out in a continuous kettle, the reaction time is 1 to 10 days.
Specifically, the reaction medium is preferably selected from one or more of aliphatic saturated hydrocarbon, aromatic hydrocarbon, aryl halide and cycloalkane, and more preferably selected from one or more of hexane, cyclohexane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene and bromobenzene.
The amount of the reaction medium used in the present invention is not particularly limited, and those skilled in the art can select an appropriate amount of the reaction medium to ensure that the polymerization reaction can proceed according to actual conditions.
Specifically, the method of polymerization preferably includes:
adding a saturated solution (the solvent in the solution is the reaction medium) containing the rare earth metal complex, the organic aluminum compound and the organic boron salt compound into a polymerization reaction system of a solution (the solvent in the solution is the reaction medium) of 1, 3-butadiene, and introducing ethylene gas.
Specifically, the method of polymerization may also preferably include:
mixing the rare earth metal complex, the organic aluminum compound, the organic boron salt compound, ethylene and 1, 3-butadiene monomer, and initiating polymerization reaction. In the present invention, ethylene is preferably continuously fed at a constant pressure during the polymerization.
Specifically, the method of polymerization may preferably further include:
specifically, it is preferable to add a methanol hydrochloric acid solution to terminate the reaction after the polymerization reaction is completed.
Specifically, after the polymerization reaction is terminated, ethanol is preferably added for separation to prepare a copolymer, and then the copolymer is dried; the drying method is preferably vacuum drying; the temperature of the drying is preferably 30 to 50 ℃, more preferably 35 to 45 ℃, and most preferably 40 ℃.
The present invention provides the use of a rare earth metal complex in the preparation of an ethylene/butadiene copolymer from ethylene and 1, 3-butadiene, and a process for preparing an ethylene/butadiene copolymer having a high breakdown voltage. The invention takes the ethylene/butadiene copolymer prepared by using the rare earth metal complex with specific structure and composition as a catalyst, and further obtains the ethylene/butadiene copolymer with specific composition and structure and high breakdown voltage. Although there is similar technology to use the rare earth metal complex in ethylene polymerization, the catalytic mechanism and technical scheme are substantially different from the present invention, and the raw materials and products are more distinct. The breakdown field strength of the ethylene/butadiene binary copolymer prepared by the rare earth metal complex catalyst is 260-370 mm/KV, the content of butadiene structural units in the copolymer is not less than 65mol%, the content of reverse 1, 4-structures in the butadiene structural units is not less than 10mol%, and the melting point of a crystalline sequence in the copolymer is 100-140 ℃. The binary copolymer of ethylene and 1, 3-butadiene prepared by the invention is a random copolymer or a multi-block copolymer containing 1, 3-butadiene monomer units and ethylene monomer units, has high content of ethylene, and has crystalline polyethylene segments with longer sequence length. The copolymer can obtain a material with low dielectric constant through crosslinking, has higher breakdown voltage, and is a novel plastic material which is not reported in the prior art such as patents, documents and the like.
The invention also provides a preparation method of the copolymer, and particularly relates to a catalyst system consisting of an amidino rare earth metal complex with a specific structure, an organic boron compound and alkyl aluminum, so that ethylene and butadiene monomers are copolymerized to obtain the ethylene/butadiene copolymer. The invention adopts two monomers of ethylene and 1, 3-butadiene with great difference in polymerization reaction mechanism and polymerization activity, and can obtain high catalytic activity to the ethylene and 1, 3-butadiene monomers by adjusting the catalyst structure and changing the polymerization reaction process.
The ethylene-butadiene provided by the invention has lower dielectric constant, can be used in an environment with higher breakdown field intensity, is a low dielectric constant material with a great development prospect, solves the application limitation of the existing ethylene-butadiene copolymer, and greatly widens the application depth and breadth.
Experimental results show that the breakdown voltage of the ethylene/butadiene copolymer provided by the invention can reach 370mm/KV at most.
To further illustrate the present invention, the following examples are provided to describe the application of the rare earth metal complex of the present invention in the preparation of ethylene/butadiene copolymer from ethylene and 1, 3-butadiene, and the preparation method of ethylene/butadiene copolymer in detail, but it should be understood that these examples are carried out in the light of the technical scheme of the present invention, and the detailed embodiments and specific procedures are given, which are only for further illustrating the features and advantages of the present invention, but not for limiting the claims of the present invention, and the scope of the present invention is not limited to the following examples.
The present invention is not particularly limited with respect to the sources of the raw materials in the following examples, and they may be prepared by a preparation method known to those skilled in the art or may be commercially available.
The complexes used in the following examples of the invention were prepared according to the methods disclosed in the J.Am.chem.Soc.2004,126,30,9182-9183 literature.
Example 1
In a glove box, 30mL of a 0.5mol/L toluene solution of butadiene was added to a 75mL glass pressure bottle, and Al was added thereto i Bu 3 (150. Mu.L, 75. Mu. Mol,0.5mol/L toluene solvent). Then, the pressure-resistant bottle was tightly capped, the glove box was taken out, and ethylene of 1.0atm was introduced under stirringThe resulting mixture was saturated in toluene to form a polymerization reaction system.
In a glove box, the complex (13.7mg, 15 mu mol) with the structure of formula 1 and Al are mixed i Bu 3 (60. Mu.L, 30. Mu. Mol,0.5mol/L toluene solvent) and triphenylcarbenium tetrakis (pentafluorophenyl) borate [ Ph 3 C][B(C 6 F 5 ) 4 ](14.4 mg, 15. Mu. Mol) was dissolved in 2mL of toluene to prepare a catalyst solution. Thereafter, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization system at 40 ℃ to initiate polymerization, after which the ethylene pressure was rapidly adjusted to 4.0atm. After 2 hours of reaction, 20mL of methanolic hydrochloric acid solution was added immediately to terminate the reaction. Then, a large amount of ethanol was added to isolate the copolymer, and the copolymer was dried under vacuum at 40 ℃ until the weight of the polymer was not changed.
The copolymer prepared in example 1 of the present invention was subjected to nmr hydrogen spectroscopy, and the results are shown in fig. 1.
FIG. 1 is a graph of a copolymer sample prepared in example 1 of the present invention 1 H NMR spectrum.
Example 2
In a glove box, 30mL of a 0.2mol/L toluene solution of butadiene was added to a 75mL glass pressure bottle, and Al was added thereto i Bu 3 (150. Mu.L, 75. Mu. Mol,0.5mol/L toluene solvent). Then, the pressure-resistant bottle was closed tightly, the glove box was taken out, and 1.0atm of ethylene was introduced under stirring to saturate it in toluene, thereby forming a polymerization reaction system.
In a glove box, a complex (15.1mg, 15 mu mol) with a structure of formula 2 and Al are mixed i Bu 3 (60. Mu.L, 30. Mu. Mol,0.5mol/L toluene solvent) and triphenylcarbenium tetrakis (pentafluorophenyl) borate [ Ph 3 C][B(C 6 F 5 ) 4 ](14.4 mg, 15. Mu. Mol) was dissolved in 2mL of toluene to prepare a catalyst solution. Thereafter, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization system at 40 ℃ to initiate polymerization, after which the ethylene pressure was rapidly adjusted to 4.0atm. After 2 hours of reaction, 20mL of methanolic hydrochloric acid solution was added immediately to terminate the reaction. Then adding a large amount of ethanol to isolate the copolymer, and drying the copolymer under vacuum at 40 deg.CPolymer until there is no change in polymer weight.
Example 3
In a glove box, 30mL of a 0.1mol/L toluene solution of butadiene was added to a 75mL glass pressure bottle, and Al was added thereto i Bu 3 (150. Mu.L, 75. Mu. Mol,0.5mol/L toluene solvent). Then, the pressure-resistant bottle was tightly closed, the glove box was taken out, and 1.0atm of ethylene was introduced with stirring to saturate it in toluene, thereby forming a polymerization reaction system.
In a glove box, the complex (13.8mg, 15. Mu. Mol) with the structure of the formula 3 and Al are mixed i Bu 3 (60. Mu.L, 30. Mu. Mol,0.5mol/L toluene solvent) and triphenylcarbenium tetrakis (pentafluorophenyl) borate [ Ph 3 C][B(C 6 F 5 ) 4 ](14.4 mg, 15. Mu. Mol) was dissolved in 2mL of toluene to prepare a catalyst solution. Thereafter, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization system at 40 ℃ to initiate polymerization, after which the ethylene pressure was rapidly adjusted to 4.0atm. After 2 hours of reaction, 20mL of methanolic hydrochloric acid solution was added immediately to terminate the reaction. Then, a large amount of ethanol was added to isolate the copolymer, and the copolymer was dried under vacuum at 40 ℃ until the weight of the polymer was not changed.
Example 4
In a glove box, 30mL of a 0.2mol/L toluene solution of butadiene was added to a 75mL glass pressure bottle, and Al was added thereto i Bu 3 (90. Mu.L, 45. Mu. Mol,0.5mol/L toluene solvent). Then, the pressure-resistant bottle was closed tightly, the glove box was taken out, and 1.0atm of ethylene was introduced under stirring to saturate it in toluene, thereby forming a polymerization reaction system.
In a glove box, the complex (14.5mg, 15. Mu. Mol) with the structure of formula 4 and Al are mixed i Bu 3 (60. Mu.L, 30. Mu. Mol,0.5mol/L toluene solvent) and triphenylcarbenium tetrakis (pentafluorophenyl) borate [ Ph 3 C][B(C 6 F 5 ) 4 ](14.4 mg, 15. Mu. Mol) was dissolved in 2mL of toluene to prepare a catalyst solution. Thereafter, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization system at 40 ℃ to initiate polymerization, after which the ethylene pressure was rapidly adjusted to4.0atm. After 2 hours of reaction, 20mL of a methanolic hydrochloric acid solution was added immediately to terminate the reaction. Then, a large amount of ethanol was added to isolate the copolymer, and the copolymer was dried under vacuum at 40 ℃ until the weight of the polymer was not changed.
Example 5
In a glove box, 30mL of a 0.2mol/L toluene solution of butadiene was added to a 75mL glass pressure bottle, and Al was added thereto i Bu 3 (90. Mu.L, 45. Mu. Mol,0.5mol/L toluene solvent). Then, the pressure-resistant bottle was closed tightly, the glove box was taken out, and 1.0atm of ethylene was introduced under stirring to saturate it in toluene, thereby forming a polymerization reaction system.
In a glove box, the complex (14.7mg, 15. Mu. Mol) with the structure of formula 5 and Al are mixed i Bu 3 (60. Mu.L, 30. Mu. Mol,0.5mol/L toluene solvent) and triphenylcarbenium tetrakis (pentafluorophenyl) borate [ Ph 3 C][B(C 6 F 5 ) 4 ](14.4 mg, 15. Mu. Mol) was dissolved in 2mL of toluene to prepare a catalyst solution. Thereafter, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization system at 40 ℃ to initiate polymerization, after which the ethylene pressure was rapidly adjusted to 4.0atm. After 6 hours of reaction, 20mL of methanolic hydrochloric acid solution was added immediately to terminate the reaction. Then, a large amount of ethanol was added to isolate the copolymer, and the copolymer was dried under vacuum at 40 ℃ until the weight of the polymer was not changed.
Example 6
To a 5L stainless steel reactor sufficiently purged with nitrogen were added 1.5L of toluene, 1, 3-butadiene (1.57mol, 85g), and Al i Bu 3 (1.04g, 5.25mmol), 1.0atm of ethylene was charged thereto with vigorous stirring to saturate it in a toluene solution, thereby forming a polymerization system.
In a glove box, a complex (0.35g, 0.375mmol) with a structure of a formula 6 and Al are put into a glove box i Bu 3 (0.75mmol, 0.15g) and triphenylcarbenium tetrakis (pentafluorophenyl) borate [ Ph 3 C][B(C 6 F 5 ) 4 ](0.36g, 0.375 mmol) was dissolved in 30mL of toluene to prepare a catalyst solution. Thereafter, the catalyst solution was taken out of the glove box and quickly added to the above at 40 ℃Polymerization was initiated in the polymerization system, and thereafter the ethylene pressure was rapidly adjusted to 10.0atm. (ii) a After 3 hours of reaction, 500mL of a methanolic hydrochloric acid solution was added immediately to terminate the reaction. Then, a large amount of ethanol was added to isolate the copolymer, and the copolymer was dried under vacuum at 40 ℃ until the weight of the polymer was not changed.
The copolymer prepared in example 6 of the present invention was subjected to nmr hydrogen spectroscopy, and the results are shown in fig. 2, and the copolymer prepared in example 6 of the present invention was subjected to nmr carbon spectroscopy, and the results are shown in fig. 3.
FIG. 2 shows a sample of a copolymer prepared in example 6 of the present invention 1 H NMR spectrum.
FIG. 3 is a sample of the copolymer prepared in example 6 of the present invention 13 C NMR spectrum.
Example 7
To a 5L stainless steel autoclave thoroughly purged with nitrogen were added 1.5L of toluene, 1, 3-butadiene (0.83mol, 45g) and Al i Bu 3 (1.04g, 5.25mmol), and 1.0atm of ethylene was charged thereto with vigorous stirring to saturate it in a toluene solution, thereby forming a polymerization system.
In a glove box, the complex with the structure of formula 7 (0.37g, 0.375mmol) and Al are mixed i Bu 3 (0.75mmol, 0.15g) and triphenylcarbenium tetrakis (pentafluorophenyl) borate [ Ph 3 C][B(C 6 F 5 ) 4 ](0.36g, 0.375 mmol) was dissolved in 30mL of toluene to prepare a catalyst solution. Thereafter, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization reaction system at 40 ℃ to initiate polymerization, after which the ethylene pressure was rapidly adjusted to 10.0atm. (ii) a After 5 hours of reaction, 500mL of a methanolic hydrochloric acid solution was added immediately to terminate the reaction. Then, a large amount of ethanol was added to isolate the copolymer, and the copolymer was dried under vacuum at 40 ℃ until the weight of the polymer was not changed.
Example 8
To a 5L stainless steel reactor sufficiently purged with nitrogen were added 1.5L of toluene, 1, 3-butadiene (0.26mol, 14g) and Al i Bu 3 (1.04g, 5.25mmol) was charged with 1.0atm ethylene under vigorous stirringSaturated in toluene solution to form a polymerization reaction system.
In a glove box, the complex with the structure of the formula 8 (0.36g, 0.375mmol) and Al are added i Bu 3 (0.75mmol, 0.15g) and triphenylcarbenium tetrakis (pentafluorophenyl) borate [ Ph 3 C][B(C 6 F 5 ) 4 ](0.36g, 0.375 mmol) was dissolved in 30mL of toluene to prepare a catalyst solution. Thereafter, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization system at 40 ℃ to initiate polymerization, after which the ethylene pressure was rapidly adjusted to 10.0atm. (ii) a After 7.3 hours of reaction, 500mL of a methanolic hydrochloric acid solution was added immediately to terminate the reaction. Then, a large amount of ethanol was added to isolate the copolymer, and the copolymer was dried under vacuum at 40 ℃ until the weight of the polymer was not changed.
Example 9
To a 5L stainless steel autoclave thoroughly purged with nitrogen were added 1.5L of toluene, 1, 3-butadiene (0.26mol, 14g) and Al i Bu 3 (0.52g, 2.63mmol), 1.0atm ethylene was charged thereto under vigorous stirring to saturate it in a toluene solution, thereby forming a polymerization system.
In a glove box, the complex with the structure of the formula 8 (0.36g, 0.375mmol) and Al are added i Bu 3 (0.75mmol, 0.15g) and triphenylcarbenium tetrakis (pentafluorophenyl) borate [ Ph 3 C][B(C 6 F 5 ) 4 ](0.36g, 0.375 mmol) was dissolved in 30mL of toluene to prepare a catalyst solution. Thereafter, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization system at 40 ℃ to initiate polymerization, after which the ethylene pressure was rapidly adjusted to 10.0atm. (ii) a After 6 hours of reaction, 500mL of a methanolic hydrochloric acid solution was added immediately to terminate the reaction. Then, a large amount of ethanol was added to isolate the copolymer, and the copolymer was dried under vacuum at 40 ℃ until there was no change in the weight of the polymer.
Determination of ethylene/butadiene copolymer composition
The content of ethylene (E) and 1, 3-Butadiene (BD) in the copolymer being determined in accordance with the ratio in C 6 D 2 Cl 4 Of copolymers measured at 110 ℃ C 1 Calculated from HNMR spectrogramTo, calculate by the following formula respectively:
f E ＝(I (1.21-1.79) -1.5*I 5.20 )/(I (1.21-1.79) +2*I (5.50-6.00) -0.5*I I5.20 )＊100％；
f BD ＝1-f E ；
ethylene/butadiene copolymer thermal Property measurement
Glass transition temperature (T) of the copolymer g ) And determination of melting point (Tm): the glass transition temperature and melting point of the copolymers were determined by Differential Scanning Calorimetry (DSC) using a Mettler TOPEM TM.
Determination of molecular weight and molecular weight distribution of ethylene/butadiene copolymer
Number average molecular weight (M) of copolymer n ) And determination of molecular weight distribution (PDI): number average molecular weight (M) of the copolymer n ) And molecular weight distribution (PDI) by Gel Permeation Chromatography (GPC) using polystyrene as standard at 150 deg.C with C 6 H 6 Cl 3 Is a mobile phase determination.
Ethylene/butadiene copolymer breakdown Voltage test
1) Cutting three polyimide films with the thickness of 150 mu m according to the length-width ratio of 20 multiplied by 20cm, and wiping the films by deionized water, ethanol and deionized water in sequence to ensure that the surfaces of the films are clean. One of the polyimide films was selected and a circular hole was formed with a radius of 2 cm.
2) Selecting 0.1884g of the powder of the ethylene/butadiene copolymer obtained in the example 9, placing the powder in a hole of a polyimide film with a hole, placing the powder on the polyimide film with the thickness of 150 mu m, and heating the powder and the polyimide film in a flat vulcanizing machine at 160 ℃ for 10 minutes;
3) After confirming that the gradient copolymer was melted, a complete 20X 20cm polyimide film was covered, and the laminated films of the gradient copolymer powder were evacuated at 160 ℃ under a pressure of 10MPa for 10 times at an evacuation interval of 3 seconds.
4) And hot pressing the ethylene/butadiene copolymer powder laminated film for 10min at the pressure of 20MPa and the temperature of 160 ℃. And after the completion, completing the rapid cooling treatment of the prepared film sample in a circulating water cooling mode to enable the sample to reach the room temperature.
5) And taking out the ethylene/butadiene copolymer film subjected to hot pressing, and annealing for 30 minutes.
6) And carrying out a breakdown test on the sample. The breakdown test was carried out using a copper ball-plate electrode, the diameter of which was 25mm. In order to prevent flashover during testing, the ball plate electrode is tightly clamped with the sample and placed in Clarity 25# transformer oil for insulation protection. When the breakdown experiment is carried out on the sample, a continuous boosting mode is adopted, and the boosting speed is 1kV/mm until the sample is broken down. Each set of breakdown experiments was repeated 6 times, and the results are shown in FIG. 4, and the breakdown voltage strength of the sample was 302KV/mm.
FIG. 4 is a graph of the mechanical properties of a copolymer sample prepared in example 7 of the present invention.
The copolymers prepared in examples 1 to 5 of the present invention were examined for their properties.
The results of examining the copolymers prepared in examples 1 to 5 are shown in Table 1.
TABLE 1 results of measuring properties of the copolymers prepared in inventive examples 1 to 5
| entry | BD/g | w t /％ | t/h | yield/g | conv. BD /％ | f E /％ | T g /T m /℃ | M n / | PDI | |
| 1 | 0.73 | 2.83 | 2 | 1.44 | 86.17 | 71.24 | -84.62/125.25 | 18.29 | 1.93 | |
| 2 | 0.32 | 1.22 | 2 | 1.04 | 42.22 | 92.87 | -/130.18 | 40.51 | 2.56 | |
| 3 | 0.15 | 0.56 | 2 | 1.32 | 36.21 | 97.88 | -/127.64 | 44.17 | 3.57 | |
| 4 | 0.44 | 1.69 | 2 | 0.54 | 44.59 | 77.29 | -/121.46 | 83.64 | 2.17 | |
| 5 | 0.44 | 1.69 | 6 | 6.49 | 70.63 | 97.47 | -/131.50 | 430.15 | 2.44 |
The copolymers prepared in examples 6 to 9 of the present invention were subjected to property testing.
The results of examining the copolymers prepared in examples 6 to 9 are shown in Table 2.
TABLE 2 results of measuring properties of the copolymers prepared in examples 6 to 9 of the present invention
| entry | BD/g | w t /％ | t/h | yield/g | conv. BD /％ | f E /％ | T g /T m /℃ | M n (kDa) | PDI |
| 6 | 85.38 | 6 | 5 | 143.89 | 79.17 | 68.52 | -97.85/124.61 | 22.91 | 2.66 |
| 7 | 44.73 | 3 | 7.3 | 126.64 | 81.99 | 82.55 | -/129.02 | 23.93 | 2.94 |
| 8 | 13.32 | 1 | 3 | 81.75 | 80.19 | 92.77 | -/125.31 | 22.38 | 2.71 |
| 9 | 13.70 | 1 | 3 | 90.51 | 80.03 | 93.33 | -/124.67 | 93.19 | 1.34 |
Referring to fig. 5, fig. 5 is a graph showing mechanical properties of a copolymer sample prepared in example 8 of the present invention.
Referring to fig. 6, fig. 6 is a graph showing breakdown voltage tests of the copolymer samples prepared in example 9 of the present invention.
The foregoing has outlined in detail the use of the rare earth metal complexes of the present invention in the preparation of ethylene/butadiene copolymers from ethylene and 1, 3-butadiene, and the preparation of ethylene/butadiene copolymers having a high breakdown voltage, wherein specific examples are set forth herein to illustrate the principles and embodiments of the present invention, but the above examples are included to help provide an understanding of the method and its underlying concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. The use of a rare earth metal complex in the preparation of an ethylene/butadiene copolymer from ethylene and 1, 3-butadiene;
the rare earth metal complex has a general formula shown in a structure of formula (I):
wherein M is one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;
R 1 、R 2 and R 3 Each independently selected from a hydrogen atom, an alkyl or haloalkyl group having 1 to 10 carbon atoms, an alkenyl or haloalkenyl group having 2 to 20 carbon atoms, an aralkyl or haloaralkyl group having 6 to 20 carbon atoms, a silyl group having 1 to 14 carbon atoms;
X 1 and X 2 Each independently selected from hydrogen, straight or branched chain aliphatic or alicyclic group having 1 to 20 carbon atoms, phenyl, straight or branched chain alkyl or ring having 1 to 20 carbon atomsPhenyl substituted by aliphatic or aromatic groups, linear or branched alkoxy containing 1 to 20 carbon atoms, linear or branched alkylamino containing 1 to 20 carbon atoms, linear or branched arylamine containing 1 to 20 carbon atoms, linear or branched silyl containing 1 to 20 carbon atoms, borohydride, allyl and allyl derivatives, halogens;
l is one selected from tetrahydrofuran, glycol dimethyl ether and pyridine;
w is an integer of 0 to 3.
2. Use according to claim 1, characterized in that the ethylene/butadiene copolymer consists of ethylene structural units and butadiene structural units;
wherein, the content of the ethylene structural unit is not less than 65mol percent, and the content of the trans-1, 4-structural unit in the butadiene structural unit is not less than 10mol percent;
the number average molecular weight of the copolymer is 10000-500000;
the ethylene/butadiene copolymer is an ethylene/butadiene copolymer containing crystalline sequences.
3. Use according to claim 1, wherein the crystalline sequences in the copolymer have a melting point of between 100 and 140 ℃;
the content of ethylene structural units in the copolymer is not less than 75mol%;
the content of trans-1, 4-structural units in butadiene structural units in the copolymer is not less than 20mol%;
the molecular weight distribution of the copolymer is not higher than 8;
the copolymer is a binary copolymer.
4. Use according to claim 1, wherein the crystalline sequences in the copolymer have a melting point of 105 to 135 ℃;
the ethylene/butadiene copolymer has a high breakdown voltage;
the breakdown field strength of the ethylene/butadiene copolymer is 260-370 mm/KV.
5. Use according to claim 1, in particular as a catalyst in a catalyst system;
the catalyst system further comprises an organoborate compound and an organoaluminum compound;
the ethylene/butadiene copolymer is prepared from ethylene and 1, 3-butadiene in a reaction medium under the action of a catalytic system;
the copolymer includes an ethylene/butadiene copolymer for a rubber material.
6. A method for preparing an ethylene/butadiene copolymer, comprising the steps of:
1) Initiating polymerization reaction of ethylene, 1, 3-butadiene and a catalyst system in a reaction medium to obtain an ethylene/butadiene binary copolymer;
the catalyst system comprises an organic boron salt compound, an organic aluminum compound and a rare earth metal complex;
the rare earth metal complex has a general formula shown in a structure of formula (I):
wherein M is one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;
R 1 、R 2 and R 3 Each independently selected from the group consisting of a hydrogen atom, an alkyl or haloalkyl group having 1 to 10 carbon atoms, an alkenyl or haloalkenyl group having 2 to 20 carbon atoms, an aralkyl or haloaralkyl group having 6 to 20 carbon atoms, a silyl group having 1 to 14 carbon atoms;
X 1 and X 2 Each independently selected from hydrogen, straight or branched chain aliphatic or alicyclic group having 1 to 20 carbon atoms, phenyl, straight or branched chain alkyl or cyclic aliphatic group having 1 to 20 carbon atoms or aromatic groupAromatic group substituted phenyl, straight chain or branched chain alkoxy containing 1 to 20 carbon atoms, straight chain or branched chain alkylamino containing 1 to 20 carbon atoms, straight chain or branched chain arylamine containing 1 to 20 carbon atoms, straight chain or branched chain silane containing 1 to 20 carbon atoms, hydroboron, allyl and allyl derivatives and halogen;
l is one selected from tetrahydrofuran, glycol dimethyl ether and pyridine;
w is an integer of 0 to 3.
7. The production method according to claim 6, characterized in that the organoboron salt compound includes an ionic compound formed of an organoboron anion and a cation, and/or an organoboron compound;
the organoboron anion includes tetraphenyl borate, tetrakis (mono-fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate ([ B (C) 6 F 5 ) 4 ] - ) Tetrakis (tetrafluoromethylphenyl) borate, tetrakis (tolyl) borate, tetrakisxylyl borate, (triphenyl, pentafluorophenyl) borate, [ tris (pentafluorophenyl), phenyl]One or more of borate and undecahydrido-7, 8-dicarbaundecaborate;
the cation comprises a carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptatrienyl cation, or ferrocenium cation containing a transition metal;
the organoboron compound includes B (C) 6 F 5 ) 3 ；
The organoaluminum compound comprises one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, and ethyldi (p-tolyl) aluminum;
the organoboron salt compound is specifically an organoboron salt compound solution.
8. The production method according to claim 6, wherein the molar ratio of the organoborate compound to the rare earth metal complex is (1 to 10): (10-1);
the molar ratio of the organic aluminum compound to the rare earth metal complex is (2-300): 1;
the pressure of the ethylene is 1 to 50 atmospheric pressures.
9. The method of claim 6, wherein the reaction medium comprises one or more of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides, and cycloalkanes;
the concentration of said 1, 3-butadiene in the reaction medium is lower than 2mol/L;
the temperature of the polymerization reaction is-20 to 150 ℃.
10. The preparation method according to claim 6, wherein the step 1) is specifically:
11 Mixing 1, 3-butadiene, a part of the organoaluminum compound solution and a reaction medium, and introducing ethylene to obtain a polymerization reaction system;
12 Mixing the rare earth metal complex solution, the other part of the organic aluminum compound, the organic boron salt compound and the reaction medium again to obtain a catalyst solution, heating the catalyst solution in the polymerization reaction system obtained in the step, increasing the pressure of ethylene, and carrying out polymerization reaction to obtain the ethylene/butadiene binary copolymer.
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