CN105061505A - Catalyst ligand, catalyst, and preparation methods and application thereof - Google Patents
Catalyst ligand, catalyst, and preparation methods and application thereof Download PDFInfo
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- CN105061505A CN105061505A CN201510593667.1A CN201510593667A CN105061505A CN 105061505 A CN105061505 A CN 105061505A CN 201510593667 A CN201510593667 A CN 201510593667A CN 105061505 A CN105061505 A CN 105061505A
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Abstract
The invention provides a catalyst ligand, a catalyst, and preparation methods and application thereof. The catalyst prepared from the ligand provided by the invention is applicable to polymerization of olefins, and is well active to homopolymerization and copolymerization of the olefins; the molecular weight of an obtained polymer is high, and the proportion of polar monomers doped during the copolymerization is higher; in addition, the catalyst provided by the invention can also catalyze the conducting of a polymerization reaction at the room temperature of 20 DEG C.
Description
Technical field
Catalyst field of the present invention, particularly relates to a kind of catalyst ligand, Catalysts and its preparation method and application.
Background technology
The character of polyolefine due to its excellence and the price of relative moderate, become the indispensable a kind of material in modern society's life.At present, polyolefinic demand is very huge, and due to the singularity of its synthetic method, the research for the core catalyzer in its synthesis also receives the extensive concern of researchist.
The history of scanning olefinic polymerization industrial development can find, technical progress invariably with the discovery of new catalyst and the successful exploitation of Technology closely relevant.In the process of olefinic polymerization, catalyzer often decide whole alkene polymerization behavior, produce the particle form of polymkeric substance and the topological framework of polymkeric substance and performance.Development for the catalyzer of olefinic polymerization makes the polymerization kind of alkene become more various, and performance is also more superior, has greatly widened the practical application area of polymkeric substance
After the initiative of the alpha-diimine nickel of Brookhart and palladium catalyst and Grubbs salicylic alidehyde imine nickel catalyzator finds, the olefinic polymerization that rear transition metal catalysis is carried out and polar monomer copolymerization cause and give more sustained attention.Recently, find to be applied to containing the neutral palladium catalyst of phosphono and sulfonic part the polyethylene that polymerising ethylene generates highly linear.This kind of catalyzer can also make ethene and surprising various polar vinyl monomer copolymerization, obtains functionalized linear copolymer.The feature that shows most of the ligand of this kind of catalyzer is by the combination containing phosphine part and a very weak σ-supplied for electronic part of a very strong σ-supplied for electronic.People generally believe, this electronics Asymmetric coordination framework effectively can suppress the elimination of β-H (X), therefore, it is possible to production of linear polymkeric substance, and have the insertion of polar monomer during making vinyl polymerization.
Due to the report that these are preliminary, each computer MSR Information system is modified to existing coordination structure and has been carried out large quantifier elimination.Several negatively charged ion bidentate ligand designs and synthesizes to asymmetric framework and corresponding neutral palladium complex.Such as, the people such as Nozaki replace phosphine part be σ supplied for electronic stronger give body NHC (N-heterocycle carbine) group, and preparation neutral NHC sulfonate palladium complex; Jordons etc., have also synthesized similar aromatic hydrocarbons bridge joint NHC sulfonate palladium mixture.Unfortunately, these two kinds of mixtures are not useable for ethylene polymerization.Jordan and Piers reports the trifluoro boron-phosphine palladium complex of bidentate independently, and it only can dimerized vinyl butylene and activity is lower.Can not the reaction of catalyzed ethylene and the copolymerization of methyl acrylate class reactive monomer when phosphine-sulfonate radical palladium (II) title complex that the catalyzer diamine base of the synthesis such as Mecking replaces is applied to vinyl polymerization.Recently, same group have studied some neutral phosphines-sulphonamide palladium (II) title complex to the impact of vinyl polymerization behavior.But what these palladium complexes had only can obtain oligomerisation of ethylene by catalyzed ethylene polymerization, and even partially catalyzed agent does not show any activity to the polymerization of ethene.
Relative to above-mentioned anion ligand, some infusive results come from the asymmetric neutral ligand of electronics and corresponding cationic catalyst.As, the result of study of the people such as Nozaki shows, cation diphosphine list oxide compound palladium complex is used for ethylene homo and has high reactivity.These mixtures also can catalyzed ethylene and some challenging polar vinyl monomer copolymerization, obtain the polymkeric substance that High Linear is functionalized, but can not the copolymerization of catalyzed ethylene and monomer methyl acrylate (MA); The people such as Jordan find to have high reactivity containing the cationic palladium catalyst of phosphine – phosphatide part at ethylene polymerization.Meanwhile, these catalyzer not only can the polymerization of catalyzed ethylene, also can catalyzed ethylene and methyl acrylate and acrylic acid copolymer, but during for copolymerization, the ratio of doping polar monomer is low; And catalytic activity is low, and the molecular weight of the polymkeric substance obtained is low.
Summary of the invention
In view of this, technical problem to be solved by this invention is to provide a kind of catalyst ligand, Catalysts and its preparation method and application, catalyst application prepared by part provided by the invention is in the polymerization of alkene, not only can the copolymerization of catalyzed alkene and acrylic monomer, and the molecular weight of the polymkeric substance obtained is high.
The invention provides a kind of catalyst ligand, there is structure shown in formula (I),
Wherein, R
1be selected from the substituted aryl of C7 ~ C30, the substituting group in described substituted aryl on aryl is the alkoxyl group of C1 ~ C12;
R
2be selected from the substituted aryl of C7 ~ C30, the substituting group in described substituted aryl on aryl is the alkoxyl group of C1 ~ C12;
R
3be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30;
R
4be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30;
R
5be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30.
Preferably, described R
1be selected from the substituted aryl of C9 ~ C18, the substituting group in described substituted aryl on aryl is the alkoxyl group of C3 ~ C8;
R
2be selected from the substituted aryl of C9 ~ C18, the substituting group in described substituted aryl on aryl is the alkoxyl group of C3 ~ C8.
Preferably, described R
3be selected from the alkyl of C3 ~ C12 or the aryl of C8 ~ C20;
R
4be selected from the alkyl of C3 ~ C12 or the aryl of C8 ~ C20;
R
5be selected from the alkyl of C3 ~ C12 or the aryl of C8 ~ C20.
Preferably, described R
1be selected from 2-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-ethoxyl phenenyl, 4-ethoxyl phenenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2-isopropyl phenyl, 4-isopropyl phenyl, 2-octyloxyphenyl, 4-octyloxyphenyl, 2-methoxyl group naphthyl, 2-ethoxynaphthyl, 2-propoxy-naphthyl, 2-isopropoxy naphthyl or 2-octyloxy naphthyl;
R
2be selected from 2-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-ethoxyl phenenyl, 4-ethoxyl phenenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2-isopropyl phenyl, 4-isopropyl phenyl, 2-octyloxyphenyl, 4-octyloxyphenyl, 2-methoxyl group naphthyl, 2-ethoxynaphthyl, 2-propoxy-naphthyl, 2-isopropoxy naphthyl or 2-octyloxy naphthyl.
Present invention also offers the preparation method of catalyst ligand shown in a kind of formula (I), comprising:
1) compound shown in the compound shown in formula (I-1) and formula (I-2) is reacted, obtains compound shown in formula (I-3),
Wherein,
R
3be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30,
R
4be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30,
R
5be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30;
2) compound shown in compound and formula (I-4) formula (I-3) Suo Shi is reacted, obtains compound shown in formula (I),
Wherein, R
1be selected from the substituted aryl of C7 ~ C30, the substituting group in the aryl of described replacement on aryl is the alkoxyl group of C1 ~ C12;
R
2be selected from the substituted aryl of C7 ~ C30, the substituting group in the aryl of described replacement on aryl is the alkoxyl group of C1 ~ C12.
Present invention also offers a kind of catalyzer, the catalyst ligand shown in contained (I).
Preferably, described catalyzer is structure shown in formula (II) or the shown structure of formula (III),
Wherein, R
1be selected from the aryl of the replacement of C7 ~ C30, the substituting group in the aryl of described replacement is the alkoxyl group of C1 ~ C12;
R
2be selected from the aryl of the replacement of C7 ~ C30, the substituting group in the aryl of described replacement is the alkoxyl group of C1 ~ C12;
R
3be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30;
R
4be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30;
R
5be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30;
R
6be selected from dimethyl sulfoxide (DMSO), pyridine or 2,5-lutidine;
X is selected from fluorine, chlorine, bromine or iodine;
X
1be selected from four-(3,5-bis-trifluoromethyl) boryl or hexafluoro tellurate radical.
Present invention also offers a kind of preparation method of catalyzer of the present invention, comprising:
Compound formula (I) Suo Shi and Pd precursor compound are reacted, obtains compound shown in formula (II);
By compound formula (II) Suo Shi and NaX
1and R
6shown compound reaction, obtains compound shown in formula (III),
Wherein, R
6be selected from dimethyl sulfoxide (DMSO), pyridine or 2,5-lutidine;
X
1be selected from four-(3,5-bis-trifluoromethyl) boryl or hexafluoro tellurate radical.
Present invention also offers the application of catalyzer of the present invention as the catalyzer of olefinic polyreaction.
Preferably, described olefinic polymerization is alkene homopolymerization or olefin-copolymerization;
Be methyl acrylate, vinyl ether, allyl acetate or chlorallylene with the monomer of olefin-copolymerization in described olefin-copolymerization.
Compared with prior art, catalyst application prepared by part provided by the invention is in the polymerization of alkene, not only there is good activity to the homopolymerization of alkene and copolymerization, and the molecular weight of the polymkeric substance obtained is high, and the ratio of the polar monomer adulterated during copolymerization is also higher, in addition, catalyzer provided by the invention can also carry out by catalytic polymerization under room temperature (20 DEG C); Experimental result shows, catalyst application provided by the invention, in the homopolymerization of ethene, can make molecular weight reach more than 10w, be applied to the copolymerization of ethene, can be that molecular weight reaches more than 20w.
Accompanying drawing explanation
Fig. 1 is the single crystal structure schematic diagram of the compound that the embodiment of the present invention 2 prepares;
Fig. 2 is the poly hydrogen spectrum that the embodiment of the present invention prepares;
Fig. 3 is the hydrogen spectrum of the ethylene copolymer that the embodiment of the present invention prepares.
Embodiment
The invention provides a kind of catalyst ligand, there is structure shown in formula (I),
Wherein, R
1be selected from the substituted aryl of C7 ~ C30, the substituting group in described substituted aryl on aryl is the alkoxyl group of C1 ~ C12;
R
2be selected from the substituted aryl of C7 ~ C30, the substituting group in described substituted aryl on aryl is the alkoxyl group of C1 ~ C12;
R
3be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30;
R
4be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30;
R
5be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30.
According to the present invention, described R
1be preferably the substituted aryl of C9 ~ C18; Wherein, the aryl in described substituted aryl is preferably phenyl or naphthyl; Substituting group in described substituted aryl on aryl is preferably the alkoxyl group of C3 ~ C8, be more preferably the alkoxyl group of C4 ~ C6, most preferably be methoxyl group, oxyethyl group, n-propyl oxygen base, sec.-propyl oxygen base, n-butoxy, isobutyl-oxygen base, tertiary butyl oxygen base, n-pentyl oxygen base or n-octyl oxygen base; In substituted aryl of the present invention, substituting group can in the optional position of aryl, and preferred substituents is positioned at ortho position or the contraposition of aryl; The present invention does not have special envoy to limit to number substituent in substituted aryl yet, is preferably 1,2,3 or 4.Concrete, described R
1for 2-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-ethoxyl phenenyl, 4-ethoxyl phenenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2-isopropyl phenyl, 4-isopropyl phenyl, 2-octyloxyphenyl or 4-octyloxyphenyl.
Described R
2be preferably the substituted aryl of C9 ~ C18; Wherein, the aryl in described substituted aryl is preferably phenyl or naphthyl; Substituting group in described substituted aryl on aryl is preferably the alkoxyl group of C3 ~ C8, be more preferably the alkoxyl group of C4 ~ C6, most preferably be methoxyl group, oxyethyl group, n-propyl oxygen base, sec.-propyl oxygen base, n-butoxy, isobutyl-oxygen base, tertiary butyl oxygen base, n-pentyl oxygen base or n-octyl oxygen base; In substituted aryl of the present invention, substituting group can in the optional position of aryl, and preferred substituents is positioned at ortho position or the contraposition of aryl; The present invention does not have special envoy to limit to number substituent in substituted aryl yet, is preferably 1,2,3 or 4.Concrete, described R
2for 2-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-ethoxyl phenenyl, 4-ethoxyl phenenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2-isopropyl phenyl, 4-isopropyl phenyl, 2-octyloxyphenyl, 4-octyloxyphenyl, 2-methoxyl group naphthyl, 2-ethoxynaphthyl, 2-propoxy-naphthyl, 2-isopropoxy naphthyl or 2-octyloxy naphthyl.
Described R
3be preferably the alkyl of C3 ~ C12 or the aryl of C8 ~ C20, wherein, described alkyl is the direct-connected alkyl of C3 ~ C12 or C3 ~ C12 branched-chain alkyl, is more preferably the direct-connected alkyl of C4 ~ C10 or C4 ~ C10 branched-chain alkyl; Described aryl is the substituted aryl of C8 ~ C20 or the unsubstituting aromatic yl of C8 ~ C20, is more preferably the substituted aryl of C9 ~ C15 or the unsubstituting aromatic yl of C9 ~ C15; More specifically, unsubstituted aryl is preferably phenyl or naphthyl; Aryl in described substituted aryl is preferably phenyl or naphthyl; Substituting group in described substituted aryl on aryl is preferably the alkoxyl group of C3 ~ C8, is more preferably the alkoxyl group of C4 ~ C6; In addition, in the present invention, in substituted aryl, substituting group can in the optional position of aryl, and preferred substituents is positioned at ortho position or the contraposition of aryl; The present invention does not have special envoy to limit to number substituent in substituted aryl yet, is preferably 1,2,3 or 4.Concrete, described R
3for methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-octyl, phenyl, 1-naphthyl, 2-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-ethoxyl phenenyl, 4-ethoxyl phenenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2-isopropyl phenyl, 4-isopropyl phenyl, 2-octyloxyphenyl, 4-octyloxyphenyl, 2-methoxyl group naphthyl, 2-ethoxynaphthyl, 2-propoxy-naphthyl, 2-isopropoxy naphthyl or 2-octyloxy naphthyl.
Described R
4be preferably the alkyl of C3 ~ C12 or the aryl of C8 ~ C20, wherein, described alkyl is the direct-connected alkyl of C3 ~ C12 or C3 ~ C12 branched-chain alkyl, is more preferably the direct-connected alkyl of C4 ~ C10 or C4 ~ C10 branched-chain alkyl; Described aryl is the substituted aryl of C8 ~ C20 or the unsubstituting aromatic yl of C8 ~ C20, is more preferably the substituted aryl of C9 ~ C15 or the unsubstituting aromatic yl of C9 ~ C15; Unsubstituted aryl is preferably phenyl or naphthyl more specifically; Aryl in described substituted aryl is preferably phenyl or naphthyl; Substituting group in described substituted aryl on aryl is preferably the alkoxyl group of C3 ~ C8, is more preferably the alkoxyl group of C4 ~ C6; In addition, in the present invention, in substituted aryl, substituting group can in the optional position of aryl, and preferred substituents is positioned at ortho position or the contraposition of aryl; The present invention does not have special envoy to limit to number substituent in substituted aryl yet, is preferably 1,2,3 or 4.Concrete, described R
4for methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-octyl, phenyl, 1-naphthyl, 2-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-ethoxyl phenenyl, 4-ethoxyl phenenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2-isopropyl phenyl, 4-isopropyl phenyl, 2-octyloxyphenyl, 4-octyloxyphenyl, 2-methoxyl group naphthyl, 2-ethoxynaphthyl, 2-propoxy-naphthyl, 2-isopropoxy naphthyl or 2-octyloxy naphthyl.
Described R
5be preferably the alkyl of C3 ~ C12 or the aryl of C8 ~ C20, wherein, described alkyl is the direct-connected alkyl of C3 ~ C12 or C3 ~ C12 branched-chain alkyl, is more preferably the direct-connected alkyl of C4 ~ C10 or C4 ~ C10 branched-chain alkyl; Described aryl is the substituted aryl of C8 ~ C20 or the unsubstituting aromatic yl of C8 ~ C20, is more preferably the substituted aryl of C9 ~ C15 or the unsubstituting aromatic yl of C9 ~ C15; Unsubstituted aryl is preferably phenyl or naphthyl more specifically; Aryl in described substituted aryl is preferably phenyl or naphthyl; Substituting group in described substituted aryl on aryl is preferably the alkoxyl group of C3 ~ C8, is more preferably the alkoxyl group of C4 ~ C6; In addition, in the present invention, in substituted aryl, substituting group can in the optional position of aryl, and preferred substituents is positioned at ortho position or the contraposition of aryl; The present invention does not have special envoy to limit to number substituent in substituted aryl yet, is preferably 1,2,3 or 4.Concrete, described R
5for methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-octyl, phenyl, 1-naphthyl, 2-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-ethoxyl phenenyl, 4-ethoxyl phenenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2-isopropyl phenyl, 4-isopropyl phenyl, 2-octyloxyphenyl, 4-octyloxyphenyl, 2-methoxyl group naphthyl, 2-ethoxynaphthyl, 2-propoxy-naphthyl, 2-isopropoxy naphthyl or 2-octyloxy naphthyl.
Present invention also offers the preparation method of the catalyst ligand of structure shown in a kind of formula (I), comprising:
1) compound shown in the compound shown in formula (I-1) and formula (I-2) is reacted, obtains compound shown in formula (I-3),
Wherein,
R
3be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30,
R
4be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30,
R
5be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30;
2) compound shown in compound and formula (I-4) formula (I-3) Suo Shi is reacted, obtains compound shown in formula (I),
Wherein, R
1be selected from the substituted aryl of C7 ~ C30, the substituting group in the aryl of described replacement on aryl is the alkoxyl group of C1 ~ C12;
R
2be selected from the aryl of the replacement of C7 ~ C30, the substituting group in the aryl of described replacement on aryl is the alkoxyl group of C1 ~ C12.
According to the present invention, the compound shown in the compound shown in formula (I-1) and formula (I-2) is reacted, obtain compound shown in formula (I-3); Wherein, the R in the compound shown in described formula (I-1)
5be preferably the alkyl of C3 ~ C12 or the aryl of C8 ~ C20, wherein, described alkyl is the direct-connected alkyl of C3 ~ C12 or C3 ~ C12 branched-chain alkyl, is more preferably the direct-connected alkyl of C4 ~ C10 or C4 ~ C10 branched-chain alkyl; Described aryl is the substituted aryl of C8 ~ C20 or the unsubstituting aromatic yl of C8 ~ C20, is more preferably the substituted aryl of C9 ~ C15 or the unsubstituting aromatic yl of C9 ~ C15; Unsubstituted aryl is preferably phenyl or naphthyl more specifically; Aryl in described substituted aryl is preferably phenyl or naphthyl; Substituting group in described substituted aryl on aryl is preferably the alkoxyl group of C3 ~ C8, is more preferably the alkoxyl group of C4 ~ C6; In addition, in the present invention, in substituted aryl, substituting group can in the optional position of aryl, and preferred substituents is positioned at ortho position or the contraposition of aryl; The present invention does not have special envoy to limit to number substituent in substituted aryl yet, is preferably 1,2,3 or 4.Concrete, described R
5for methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-octyl, phenyl, 1-naphthyl, 2-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-ethoxyl phenenyl, 4-ethoxyl phenenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2-isopropyl phenyl, 4-isopropyl phenyl, 2-octyloxyphenyl, 4-octyloxyphenyl, 2-methoxyl group naphthyl, 2-ethoxynaphthyl, 2-propoxy-naphthyl, 2-isopropoxy naphthyl or 2-octyloxy naphthyl, R in compound shown in described formula (I-2)
3, R
4independently be preferably the alkyl of C3 ~ C12 or the aryl of C8 ~ C20, wherein, described alkyl is the direct-connected alkyl of C3 ~ C12 or C3 ~ C12 branched-chain alkyl, is more preferably the direct-connected alkyl of C4 ~ C10 or C4 ~ C10 branched-chain alkyl, described aryl is the substituted aryl of C8 ~ C20 or the unsubstituting aromatic yl of C8 ~ C20, is more preferably the substituted aryl of C9 ~ C15 or the unsubstituting aromatic yl of C9 ~ C15, unsubstituted aryl is preferably phenyl or naphthyl more specifically, aryl in described substituted aryl is preferably phenyl or naphthyl, substituting group in described substituted aryl on aryl is preferably the alkoxyl group of C3 ~ C8, is more preferably the alkoxyl group of C4 ~ C6, in addition, in the present invention, in substituted aryl, substituting group can in the optional position of aryl, and preferred substituents is positioned at ortho position or the contraposition of aryl, the present invention does not have special envoy to limit to number substituent in substituted aryl yet, is preferably 1,2,3 or 4.Concrete, described R
3, R
4independently be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-octyl, phenyl, 1-naphthyl, 2-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-ethoxyl phenenyl, 4-ethoxyl phenenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2-isopropyl phenyl, 4-isopropyl phenyl, 2-octyloxyphenyl, 4-octyloxyphenyl, 2-methoxyl group naphthyl, 2-ethoxynaphthyl, 2-propoxy-naphthyl, 2-isopropoxy naphthyl or 2-octyloxy naphthyl.The mol ratio of the compound shown in the compound shown in described formula (I-1) and described formula (I-2) is preferably (1 ~ 1.2): 1.
Concrete, the present invention's reaction is specially: the compound shown in the compound shown in formula (I-1) and formula (I-2) is first carried out substitution reaction, and then is oxidized, and obtains compound shown in formula (I-3); Wherein, described substitution reaction is reacted under organic bases existence condition, and described organic bases is preferably tertiary amine; The temperature of described reaction is preferably 10 ~ 120 DEG C, is more preferably 30 ~ 80 DEG C; The oxygenant of described oxidizing reaction is preferably 30wt% aqueous hydrogen peroxide solution, and the temperature of described oxidizing reaction is preferably-60 ~-10 DEG C.
According to the present invention, the compound shown in compound and formula (I-4) formula (I-3) Suo Shi also reacts by the present invention, obtains compound shown in formula (I), wherein, and the described R in formula (I-4)
1, R
2independently be preferably the substituted aryl of C9 ~ C18; Wherein, the aryl in described substituted aryl is preferably phenyl or naphthyl; Substituting group in described substituted aryl on aryl is preferably the alkoxyl group of C3 ~ C8, be more preferably the alkoxyl group of C4 ~ C6, most preferably be methoxyl group, oxyethyl group, n-propyl oxygen base, sec.-propyl oxygen base, n-butoxy, isobutyl-oxygen base, tertiary butyl oxygen base, n-pentyl oxygen base or n-octyl oxygen base; In substituted aryl of the present invention, substituting group can in the optional position of aryl, and preferred substituents is positioned at ortho position or the contraposition of aryl; The present invention does not have special envoy to limit to number substituent in substituted aryl yet, is preferably 1,2,3 or 4.Concrete, described R
1, R
2independently be selected from 2-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-ethoxyl phenenyl, 4-ethoxyl phenenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2-isopropyl phenyl, 4-isopropyl phenyl, 2-octyloxyphenyl, 4-octyloxyphenyl, 2-methoxyl group naphthyl, 2-ethoxynaphthyl, 2-propoxy-naphthyl, 2-isopropoxy naphthyl or 2-octyloxy naphthyl; The mol ratio of the compound shown in the compound shown in described formula (I-3) and described formula (I-4) is preferably (1 ~ 1.2): 1; Alkali in described reaction is preferably organic bases and butyllithium, and described organic bases is preferably Tetramethyl Ethylene Diamine (TMEDA); The temperature of described reaction is preferably-90 ~-60 DEG C; The solvent of described reaction be preferably in toluene or tetrahydrofuran (THF) one or both.
Present invention also offers a kind of catalyzer, comprise the part of structure shown in formula (I), described catalyzer preferably has structure shown in structure shown in formula (II) or formula (III),
Wherein, R
1be selected from the aryl of the replacement of C7 ~ C30, the substituting group in the aryl of described replacement is the alkoxyl group of C1 ~ C12;
R
2be selected from the aryl of the replacement of C7 ~ C30, the substituting group in the aryl of described replacement is the alkoxyl group of C1 ~ C12;
R
3be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30;
R
4be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30;
R
5be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30;
R
6be selected from dimethyl sulfoxide (DMSO), pyridine or 2,5-lutidine;
X is selected from fluorine, chlorine, bromine or iodine;
X
1be selected from four-(3,5-bis-trifluoromethyl) boryl or be hexafluoro tellurate radical (SbF
6 -).
According to the present invention, described R
1be preferably the substituted aryl of C9 ~ C18; Wherein, the aryl in described substituted aryl is preferably phenyl or naphthyl; Substituting group in described substituted aryl on aryl is preferably the alkoxyl group of C3 ~ C8, be more preferably the alkoxyl group of C4 ~ C6, most preferably be methoxyl group, oxyethyl group, n-propyl oxygen base, sec.-propyl oxygen base, n-butoxy, isobutyl-oxygen base, tertiary butyl oxygen base, n-pentyl oxygen base or n-octyl oxygen base; In substituted aryl of the present invention, substituting group can in the optional position of aryl, and preferred substituents is positioned at ortho position or the contraposition of aryl; The present invention does not have special envoy to limit to number substituent in substituted aryl yet, is preferably 1,2,3 or 4.Concrete, described R
1for 2-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-ethoxyl phenenyl, 4-ethoxyl phenenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2-isopropyl phenyl, 4-isopropyl phenyl, 2-octyloxyphenyl or 4-octyloxyphenyl.
Described R
2be preferably the substituted aryl of C9 ~ C18; Wherein, the aryl in described substituted aryl is preferably phenyl or naphthyl; Substituting group in described substituted aryl on aryl is preferably the alkoxyl group of C3 ~ C8, be more preferably the alkoxyl group of C4 ~ C6, most preferably be methoxyl group, oxyethyl group, n-propyl oxygen base, sec.-propyl oxygen base, n-butoxy, isobutyl-oxygen base, tertiary butyl oxygen base, n-pentyl oxygen base or n-octyl oxygen base; In substituted aryl of the present invention, substituting group can in the optional position of aryl, and preferred substituents is positioned at ortho position or the contraposition of aryl; The present invention does not have special envoy to limit to number substituent in substituted aryl yet, is preferably 1,2,3 or 4.Concrete, described R
2for 2-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-ethoxyl phenenyl, 4-ethoxyl phenenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2-isopropyl phenyl, 4-isopropyl phenyl, 2-octyloxyphenyl, 4-octyloxyphenyl, 2-methoxyl group naphthyl, 2-ethoxynaphthyl, 2-propoxy-naphthyl, 2-isopropoxy naphthyl or 2-octyloxy naphthyl.
Described R
3be preferably the alkyl of C3 ~ C12 or the aryl of C8 ~ C20, wherein, described alkyl is the direct-connected alkyl of C3 ~ C12 or C3 ~ C12 branched-chain alkyl, is more preferably the direct-connected alkyl of C4 ~ C10 or C4 ~ C10 branched-chain alkyl; Described aryl is the substituted aryl of C8 ~ C20 or the unsubstituting aromatic yl of C8 ~ C20, is more preferably the substituted aryl of C9 ~ C15 or the unsubstituting aromatic yl of C9 ~ C15; More specifically, unsubstituted aryl is preferably phenyl or naphthyl; Aryl in described substituted aryl is preferably phenyl or naphthyl; Substituting group in described substituted aryl on aryl is preferably the alkoxyl group of C3 ~ C8, is more preferably the alkoxyl group of C4 ~ C6; In addition, in the present invention, in substituted aryl, substituting group can in the optional position of aryl, and preferred substituents is positioned at ortho position or the contraposition of aryl; The present invention does not have special envoy to limit to number substituent in substituted aryl yet, is preferably 1,2,3 or 4.Concrete, described R
3for methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-octyl, phenyl, 1-naphthyl, 2-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-ethoxyl phenenyl, 4-ethoxyl phenenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2-isopropyl phenyl, 4-isopropyl phenyl, 2-octyloxyphenyl, 4-octyloxyphenyl, 2-methoxyl group naphthyl, 2-ethoxynaphthyl, 2-propoxy-naphthyl, 2-isopropoxy naphthyl or 2-octyloxy naphthyl.
Described R
4be preferably the alkyl of C3 ~ C12 or the aryl of C8 ~ C20, wherein, described alkyl is the direct-connected alkyl of C3 ~ C12 or C3 ~ C12 branched-chain alkyl, is more preferably the direct-connected alkyl of C4 ~ C10 or C4 ~ C10 branched-chain alkyl; Described aryl is the substituted aryl of C8 ~ C20 or the unsubstituting aromatic yl of C8 ~ C20, is more preferably the substituted aryl of C9 ~ C15 or the unsubstituting aromatic yl of C9 ~ C15; Unsubstituted aryl is preferably phenyl or naphthyl more specifically; Aryl in described substituted aryl is preferably phenyl or naphthyl; Substituting group in described substituted aryl on aryl is preferably the alkoxyl group of C3 ~ C8, is more preferably the alkoxyl group of C4 ~ C6; In addition, in the present invention, in substituted aryl, substituting group can in the optional position of aryl, and preferred substituents is positioned at ortho position or the contraposition of aryl; The present invention does not have special envoy to limit to number substituent in substituted aryl yet, is preferably 1,2,3 or 4.Concrete, described R
4for methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-octyl, phenyl, 1-naphthyl, 2-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-ethoxyl phenenyl, 4-ethoxyl phenenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2-isopropyl phenyl, 4-isopropyl phenyl, 2-octyloxyphenyl, 4-octyloxyphenyl, 2-methoxyl group naphthyl, 2-ethoxynaphthyl, 2-propoxy-naphthyl, 2-isopropoxy naphthyl or 2-octyloxy naphthyl.
Described R
5be preferably the alkyl of C3 ~ C12 or the aryl of C8 ~ C20, wherein, described alkyl is the direct-connected alkyl of C3 ~ C12 or C3 ~ C12 branched-chain alkyl, is more preferably the direct-connected alkyl of C4 ~ C10 or C4 ~ C10 branched-chain alkyl; Described aryl is the substituted aryl of C8 ~ C20 or the unsubstituting aromatic yl of C8 ~ C20, is more preferably the substituted aryl of C9 ~ C15 or the unsubstituting aromatic yl of C9 ~ C15; Unsubstituted aryl is preferably phenyl or naphthyl more specifically; Aryl in described substituted aryl is preferably phenyl or naphthyl; Substituting group in described substituted aryl on aryl is preferably the alkoxyl group of C3 ~ C8, is more preferably the alkoxyl group of C4 ~ C6; In addition, in the present invention, in substituted aryl, substituting group can in the optional position of aryl, and preferred substituents is positioned at ortho position or the contraposition of aryl; The present invention does not have special envoy to limit to number substituent in substituted aryl yet, is preferably 1,2,3 or 4.Concrete, described R
5for methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-octyl, phenyl, 1-naphthyl, 2-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-ethoxyl phenenyl, 4-ethoxyl phenenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2-isopropyl phenyl, 4-isopropyl phenyl, 2-octyloxyphenyl, 4-octyloxyphenyl, 2-methoxyl group naphthyl, 2-ethoxynaphthyl, 2-propoxy-naphthyl, 2-isopropoxy naphthyl or 2-octyloxy naphthyl.
R
6be preferably dimethyl sulfoxide (DMSO).
Described X is preferably chlorine, bromine or iodine.
Present invention also offers a kind of preparation method of catalyzer, comprising:
Compound formula (I) Suo Shi and Pd precursor compound are reacted, obtains compound shown in formula (II);
By compound formula (II) Suo Shi and NaX
1and R
6shown compound reaction, obtains compound shown in formula (III),
Wherein, R
6be selected from dimethyl sulfoxide (DMSO), pyridine or 2,5-lutidine;
X
1be selected from four-(3,5-bis-trifluoromethyl) boryl or hexafluoro tellurate ion.
According to the present invention, compound formula (I) Suo Shi and Pd precursor compound react by the present invention, obtain compound shown in formula (II); Described Pd precursor compound is preferably Pd (COD) MeCl or Pd (COD) MeBr, and wherein, described COD is cyclooctadiene; The condition of the present invention to reaction is not particularly limited, preparation method well known in the art.
According to the present invention, by compound formula (II) Suo Shi and NaX
1and R
6shown compound reaction, obtain compound shown in formula (III), described X is preferably chlorine, bromine or iodine; Described R
6be preferably dimethyl sulfoxide (DMSO).The condition of the present invention to reaction is not particularly limited, preparation method well known in the art.
Catalyst application prepared by part provided by the invention, in the polymerization of alkene, shows high thermostability and activity; Not only there is good activity to the homopolymerization of alkene and copolymerization, and the molecular weight of the polymkeric substance obtained is high, and the ratio of the polar monomer adulterated during copolymerization is also higher, in addition, catalyzer provided by the invention can also carry out by catalytic polymerization under room temperature (20 DEG C).
Present invention also offers the application as the catalyzer of olefinic polyreaction of a kind of formula (II) or the catalyzer shown in formula (III).In the present invention, described alkene is preferably one or more in ethene, propylene and butylene, is more preferably ethene; Described olefinic polymerization comprises alkene homopolymerization and olefin-copolymerization, is preferably methyl acrylate, vinyl ether, allyl acetate or chlorallylene in described olefin-copolymerization with the monomer of olefin-copolymerization.
When the polymerization process of alkene provided by the invention is used for the homopolymerization of alkene, the polymkeric substance obtained not only molecular weight is large, and the degree of branching is low, and polyreaction can be carried out in room temperature, and reactive behavior is high.During copolymerization for alkene and bioactive molecule, the molecular weight of the polymkeric substance not only obtained is high, and the doping ratio of bioactive molecule is also high, and polyreaction also can be carried out in room temperature.
Technical scheme below in conjunction with the embodiment of the present invention is clearly and completely described, and obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
In the present invention, all materials to water and air sensitivity all leave in glove box, and all solvents all dewater through super-dry, and ethylene gas is by the deoxygenation pillar purifying that dewaters, and methyl acrylate is purified by the deoxygenation distillation under vacuum that dewaters.Be not particularly illustrated, rear direct use bought by all raw materials, and the source chemicals in experimentation is purchased from An Naiji, lark prestige and Aladdin.
Silicagel column is separated with 200-300 object silica gel, and nuclear-magnetism detects with Bruker400MHz nuclear-magnetism instrument.Ultimate analysis is measured by China Science & Technology University's physics and chemistry center.Molecular weight and molecualr weight distribution is measured by high temperature GPC.Mass spectrum ThermoLTQOrbitrapXL (ESI+) or P-SIMS-GlyofBrukerDaltonicsInc (EI+) measures.Single crystal X diffraction analysis adopts OxfordDiffractionGeminiSUltraCCD single crystal diffraction instrument, CuK α
room temperature radiation.
Embodiment 1
P-(2-(two (2-p-methoxy-phenyl) phosphino-) phenyl)-N, N-di-isopropyl P-phenyl time acid amides
Diphenyl phosphorus chloride (16.3 milliliters, 0.09 mole) join containing suitable dialkylamine (0.09 mole, 1.0 equivalent, R: sec.-propyl, ethyl) and triethylamine (0.18 mole, 2.0 equivalents) toluene (250 milliliters) solution in, at 0 DEG C, mixture at room temperature stirs 8 hours, be cooled to-10 DEG C afterwards, and added the H of 30%
2o
24.475 grams of sulphur are added in (15 milliliters) or solution.Again mixture is stirred 12 hours.Solvent is evaporated, by product dichloromethane extraction.Use washed with diethylether afterwards, collect white solid, obtain required time pure phosphonic amide N, N-di-isopropyl diphenylphosphine acid amides, it is white solid, and yield is 80%.
To containing N, 20 milliliters of toluene of N-di-isopropyl diphenylphosphine acid amides (2.31 mmole) and TMEDA (0.49 milliliter, 2.54 mmoles) solution in the solution (1.0 milliliters of slow instillation n-Butyl Lithium, 2.4 molar solutions in normal hexane, 2.4 mmoles), keep solution Bao Chi – 80oC in adition process.After one hour, the toluene solution of diaryl phosphine chlorine (aryl: o-methoxyphenyl, 2.54 mmoles) injects above-mentioned reaction solution.To react at room temperature stir 2 hours, then pour in frozen water, with methylene dichloride (3 × 15 milliliters) extraction, with Sulfothiorine (2 × 15 milliliters) washing, through anhydrous sodium sulfate drying and under vacuo drying obtain light yellow solid.By column chromatography eluting, use the silicagel column of 200-300 object silica gel to be separated, wherein first use the mixture of sherwood oil and ethyl acetate 1:1 as moving phase, obtain solid and the shown compound of formula (I) of white.Output: 0.71 gram, yield is 60%.
Carry out nuclear-magnetism detection to the compound obtained, result is as follows:
1hNMR (400MHz, CDCl
3): δ 8.01 (s, 1H, aryl-H), 7.68 – 7.60 (m, 2H, aryl-H), 7.39 (t, J=7.1Hz, 1H, aryl-H), 7.28 (dd, J=9.3,3.2Hz, 1H, aryl-H), 7.22 (dd, J=11.4,4.1Hz, 3H, aryl-H), 7.15 (td, J=7.5,3.0Hz, 2H, aryl-H), 7.06 – 6.97 (m, 1H, aryl-H), 6.80 – 6.71 (m, 4H, aryl-H), 6.56 (ddd, J=7.4,3.8,1.5Hz, 1H, aryl-H), 6.46 (s, 1H, aryl-H), 3.65 (dd, J=14.6,7.5Hz, 2H ,-CH (CH
3)
2), 3.57 (d, J=19.2Hz, 6H ,-OCH
3), 1.30 (d, J=6.7Hz, 6H ,-CH (CH
3)
2), 1.26 (d, J=6.8Hz, 6H ,-CH (CH
3)
2).
31PNMR(162MHz,CDCl
3):δ32.74(d,J＝3.7Hz),-27.95(s)。
13CNMR(101MHz,CDCl
3):δ160.87(t,J＝16.2Hz),136.95(s),135.70(d,J＝1.7Hz),135.57(d,J＝12.5Hz),134.08(d,J＝13.6Hz),133.66(dd,J＝10.7,7.3Hz),132.43(dd,J＝10.0,2.3Hz),130.78(d,J＝2.6Hz),130.42(d,J＝2.8Hz),129.45(d,J＝10.2Hz),127.54(d,J＝11.9Hz),127.21(d,J＝12.6Hz),126.46(d,J＝17.2Hz),120.65(d,J＝3.8Hz),110.45(s),109.76(s),55.60(s,-OCH
3),55.14(s,-OCH
3),47.41(d,J＝3.8Hz,-CH(CH
3)
2),23.70(d,J＝2.0Hz,-CH(CH
3)
2)。
Carry out mass spectrometric detection to the compound obtained, result shows: HRMS (m/z): calculate C
32h
37nO
3p
2: 545.2249, actual measurement 546.2312 [M+H]+.
In addition: R
1, R
2, R
3and R
4the synthetic method of the different title complex of substituting group identical with this method, also synthesize following compound by this method:
Embodiment 2
[o-((o-OMePh)
2p) C
6h
4(P (O) (N (iPr)
2) Ph)] synthesis of Pd (Me) (Cl) palladium complex
Shown in formula (I), part (1 mole) and (COD) PdMeCl (252 milligrams, 0.96 mmole) are weighed into and are placed in a bottle of bench-top.Methylene dichloride (5 milliliters) joins in this solid, and mixture is at room temperature stirred 1 hour.After crossing diatomite, normal hexane is layered on filtrate, leaves standstill.After several hours, light yellow crystalline solid is formed, by collecting by filtration, with in hexanes wash (3 × 2mL), and dry under vacuo, obtain light yellow solid and be the compound shown in formula (II-1).Yield is 78%.
Carry out nuclear-magnetism detection to the compound obtained, result is as follows:
1hNMR (400MHz, CDCl
3): δ 7.94 (s, 1H, aryl-H), 7.52 – 7.35 (m, 4H, aryl-H), 7.27 (d, J=6.3Hz, 4H, aryl-H), 7.12 (s, 3H, aryl-H), 6.90 – 6.76 (m, 4H, aryl-H), 6.65 (s, 1H, aryl-H), 3.58 (d, J=39.3Hz, 8H), 1.25 (t, J=14.0Hz, 12H ,-CH (CH
3)
2), 0.37 (s, 3H, Pd-CH
3).
13CNMR(101MHz,CDCl
3):δ160.67(s),160.29(d,J＝4.9Hz),135-137(br),133-135(br),133.05(d,J＝9.0Hz),132.55(s),131.61(d,J＝2.5Hz),131.15(s),129-131(br),128.82(d,J＝11.6Hz),127.91(d,J＝12.8Hz),120.67(d,J＝9.0Hz),116.16(d,J＝52.4Hz),111.07(s),110.88(d,J＝4.8Hz),55.53(s,-OCH
3),48.44(d,J＝3.2Hz,-CH(CH
3)
2),23.81(d,J＝3.0Hz,-CH(CH
3)
2),23.61(s,-CH(CH
3)
2),-1.65(s,Pd-CH
3)。
31PNMR(162MHz,CDCl
3):δ32.98(d,J＝192.9Hz),27.54(s),19.36(s)。
Ultimate analysis is carried out to the compound obtained: calculate C
33h
40clNO
3p
2pd:C, 56.42; H, 5.74; N, 1.99; Actual C, 56.47; H, 5.77; N, 2,21.
Single crystal diffraction is carried out to the compound that embodiment 2 obtains, the results are shown in Figure the single crystal structure schematic diagram that 1, Fig. 1 is the compound that the embodiment of the present invention 2 prepares.
Comparative example 1
[o-(Cy
2p) C
6h
4(P (O) (N (iPr)
2) Ph)] synthesis of Pd (Me) (Cl) palladium complex
Shown in formula (I-d1), part (1 mole) and (COD) PdMeCl (252 milligrams, 0.96 mmole) are weighed into and are placed in a bottle of bench-top.Methylene dichloride (5 milliliters) joins in this solid, and mixture is at room temperature stirred 1 hour.After crossing diatomite, normal hexane is layered on filtrate, leaves standstill.After several hours, light yellow crystalline solid is formed, by collecting by filtration, with in hexanes wash (3 × 2mL), and dry under vacuo, obtain light yellow solid, i.e. compound shown in formula (II-d1).Yield is 80%.
Carry out nuclear-magnetism detection to the compound obtained, result is as follows:
1hNMR (400MHz, CDCl
3): δ 8.16 – 8.06 (m, 2H, aryl-H), 8.03 (ddd, J=13.0,5.8,3.4Hz, 1H, aryl-H), 7.80 (s, 1H, aryl-H), 7.66 (d, J=4.4Hz, 2H, aryl-H), 7.56 – 7.42 (m, 3H, aryl-H), 3.43 (ddt, J=20.4,13.5,6.7Hz, 2H ,-CH (CH
3)
2), 2.23 (dd, J=24.1,12.0Hz, 1H, cyclohexyl), 2.07 (ddd, J=12.5,11.1,4.6Hz, 1H, cyclohexyl), 1.95 (t, J=12.2Hz, 1H, cyclohexyl), 1.81 (dd, J=28.9,12.7Hz, 4H, cyclohexyl), 1.68 (dd, J=19.6,10.9Hz, 4H, cyclohexyl), 1.52 (d, J=10.7Hz, 1H, cyclohexyl), 1.44 – 1.33 (m, 2H, cyclohexyl), 1.29 (dd, J=11.8,8.6Hz, 3H, cyclohexyl), 1.23 (d, J=6.8Hz, 6H ,-CH (CH
3)
2), 1.19 (d, J=6.7Hz, 6H ,-CH (CH
3)
2), 1.10 (dd, J=20.5,7.9Hz, 2H, cyclohexyl), 0.90 (dt, J=19.2,13.0Hz, 2H, cyclohexyl), 0.53 (d, J=2.1Hz, 3H, Pd-CH
3), 0.12 (dt, J=21.4,8.0Hz, 1H, cyclohexyl).
13CNMR(101MHz,CDCl
3):δ140.54(d,J＝12.4Hz),139.30(d,J＝12.4Hz),134.75(d,J＝9.9Hz),134.28(t,J＝11.6Hz),134.03–133.61(m),132.53(s),132.31(d,J＝2.7Hz),131.31(s),130.93(s),129.43(d,J＝11.4Hz),128.03(d,J＝13.1Hz),48.39(d,J＝4.2Hz,-CH(CH
3)
2),37.59(d,J＝24.9Hz,Cy),34.37(d,J＝24.3Hz,Cy),29.59–29.01(m,Cy),28.13(d,J＝6.1Hz,Cy),27.62–26.66(m,Cy),25.94(d,J＝15.6Hz,Cy),24.03(d,J＝1.5Hz,-CH(CH
3)
2),22.99(d,J＝2.9Hz,-CH(CH
3)
2),-6.05(s,Pd-CH
3)。
31PNMR(162MHz,CDCl
3):δ38.73(d,J＝12.7Hz),33.44(d,J＝12.7Hz)。
Carry out ultimate analysis to the compound obtained, result shows, calculates C
31h
48clNOP
2pd:C, 56.89; H, 7.39; N, 2.14; Actual C, 57.03; H, 7.38; N, 2.31.
Comparative example 2:
[o-(Ph
2p) C
6h
4(P (S) (N (iPr)
2) Ph)] synthesis of Pd (Me) (Cl) palladium complex
To containing N, N-di-isopropyl phenylbenzene sulfo-phosphonic amide (300 milligrams, 0.946 mmole) and TMEDA (0.71 milliliter, in 0 DEG C of solution of the anhydrous diethyl ether (30 milliliters) of 4.73 mmoles) add n-butyllithium solution (0.89 milliliter of 1.6M hexane solution, 1.42 mmoles).React after 2 hours at 0 DEG C, add the Chlorodiphenylphosphine (1.42 mmole) of 1.5 equivalents.Reaction mixture is stirred 2 hours at 0 DEG C, then uses methyl alcohol cancellation.Reaction mixture is poured into water, and extracts with methylene dichloride (2 × 15 milliliters).By organic layer through dried over sodium sulfate and vacuum concentration.Crude mixture obtains white powder by column chromatography (silica gel, ethyl acetate/PE, 1:1), is sulfur-containing ligand.
The sulfur-containing ligand (1 mole) obtained and (COD) PdMeCl (252 milligrams, 0.96 mmole) are weighed into and are placed in a bottle of bench-top.Methylene dichloride (5 milliliters) joins in this solid, and mixture is at room temperature stirred 1 hour.After crossing diatomite, normal hexane is layered on filtrate, leaves standstill.After several hours, light yellow crystalline solid is formed, by collecting by filtration, with in hexanes wash (3 × 2mL), and dry under vacuo, obtain light yellow solid, i.e. compound shown in formula (II-d2), yield is 79%.
Carry out nuclear-magnetism detection to the compound obtained, result is as follows:
1hNMR (400MHz, CDCl3): δ 8.36 – 8.13 (m, 1H, aryl-H), 7.66 (dd, J=13.7,7.6Hz, 3H, aryl-H), 7.55 (t, J=7.4Hz, 1H, aryl-H), 7.43 – 7.18 (m, 8H, aryl-H), 7.04 (dd, J=9.2,5.3Hz, 6H, aryl-H), 3.79 – 3.54 (m, 2H ,-CH (CH3) 2), 1.27 (d, J=6.7Hz, 6H,-CH (CH3) 2), 1.11 (d, J=6.7Hz, 6H ,-CH (CH3) 2), 0.49 (d, J=2.9Hz, 3H, Pd-CH3).
13CNMR(101MHz,CDCl3):δ138.67(d,J＝13.4Hz),138.09(d,J＝12.0Hz),137.77(t,J＝12.5Hz),137.43(d,J＝11.4Hz),134.90(d,J＝13.6Hz),134.27(d,J＝11.9Hz),133.36(s),132.93(d,J＝11.8Hz),132.82(s),132.69(d,J＝2.9Hz),132.54(d,J＝7.8Hz),131.55(dd,J＝6.2,2.4Hz),130.95(s),130.31(d,J＝2.1Hz),129.97(s),129.59(d,J＝9.4Hz),128.31(t,J＝11.4Hz),127.94(d,J＝13.3Hz),127.77(s),49.67(d,J＝4.1Hz,-CH(CH3)2),23.45(d,J＝2.5Hz,-CH(CH3)2),23.31(d,J＝1.7Hz,-CH(CH3)2),11.39(s,Pd-CH3)。
31PNMR(162MHz,CDCl3):δ61.99(d,J＝26.4Hz),31.01(d,J＝26.4Hz)。
Carry out ultimate analysis to the compound obtained, result shows: ultimate analysis calculates C
31h
36clNP
2pdS:C, 56.54; H, 5.51; N, 2.13; Actual C, 56.85; H, 5.43; N, 2.17.
Embodiment 3
The synthesis of { [o-((o-OMePh) 2P) C6H4 (P (O) (N (iPr) 2) Ph)] Pd (Me) (DMSO) }+BAF-palladium cationic complexes
Title complex (0.25 mmole) shown in loading type (II-1) in bottle, NaBAF (0.25 mmole), dimethyl sulfoxide (DMSO) (0.25 mmole), then adds methylene dichloride (2 milliliters).By the yellow solution vigorous stirring obtained, after at room temperature 40 minutes.By diatomite filtration, obtain the yellow solution clarified.Under vacuo except desolventizing, obtaining light yellow solid, is compound formula (III-1) Suo Shi.Yield is 62%.
Carry out nuclear-magnetism detection to the compound obtained, result is as follows:
1hNMR (400MHz, CDCl3): δ 8.02 – 7.92 (m, 1H, aryl-H), 7.71 (s, 8H, aryl-H), 7.59 (d, J=7.5Hz, 2H, aryl-H), 7.52 (s, 5H, aryl-H), 7.45 (d, J=7.4Hz, 2H, aryl-H), 7.38 – 7.27 (m, 4H, aryl-H), 7.18 (s, 3H, aryl-H), 6.95 (dd, J=13.3,7.6Hz, 3H, aryl-H), 6.60 (s, 3H, aryl-H), 3.69 (s, 3H), 3.47 (s, 5H), 2.76 (s, 6H, DMSO), 1.20 (d, J=6.6Hz, 12H ,-CH (CH
3)
2), 0.18 (s, 3H, Pd-CH
3).
13CNMR(101MHz,CDCl
3):δ162.61(s),162.12(s),161.62(s),161.13(s),160.31(s),159.95(s),136.02(s),134.96(s),134.17(s),133.78(s),133.05(s),132.28(d,J＝9.9Hz),131.38(s),130.02(d,J＝13.8Hz),129.53(s),129.22(s),128.71(dd,J＝27.0,14.6Hz),126.06(s),123.35(s),121.19(t,J＝13.0Hz),120.64(s),117.62(s),111.39(d,J＝31.6Hz),55.56(s,-OCH
3),54.87(s,-OCH
3),48.66(s,-CH(CH
3)
2),40.05(s,DMSO),23.86(s,-CH(CH
3)
2),22.98(s,-CH(CH
3)
2),3.50(s,Pd-CH
3).
31PNMR(162MHz,CDCl
3):δ40.80,29.95.
Carry out mass analysis to the compound obtained, result is as follows: ESI-mass spectrum: (CH
3cN, positively charged ion scans): 666.1512 ([M-DMSO-BAF
-]
+).
Carry out ultimate analysis to the compound obtained, result is as follows: ultimate analysis calculates C
67h
58bF
24nO
4p
2pdS:C, 50.03; H, 3.63; N, 0.87; Actual C, 50.22; H, 3.55; N, 0.96.
Comparative example 3
{ [o-(Cy2P) C6H4 (P (O) (N (iPr)
2) Ph)] Pd (Me) (DMSO)
+bAF
-the synthesis of palladium cationic complexes
Compound (0.25 mmole) shown in loading type (II-d1) in bottle, NaBAF (0.25 mmole), dimethyl sulfoxide (DMSO) (0.25 mmole), then adds methylene dichloride (2 milliliters).By the yellow solution vigorous stirring obtained, after at room temperature 40 minutes.By diatomite filtration, obtain the yellow solution clarified.Under vacuo except desolventizing, obtain shallow white solid, be the compound shown in formula (III-d1).Yield is 67%;
Carry out nuclear-magnetism detection to the compound obtained, result is as follows:
1hNMR (400MHz, CDCl
3): δ 8.09 (s, 1H, aryl-H), 7.73 (s, 11H, aryl-H), 7.66 (s, 2H, aryl-H), 7.54 (s, 5H, aryl-H), 7.48 (d, J=4.4Hz, 2H, aryl-H), 3.53 – 3.34 (m, 2H ,-CH (CH
3)
2), 2.85 (s, 6H, DMSO), 2.39 – 2.17 (m, 2H, cyclohexyl), 1.99 (s, 1H, cyclohexyl), 1.89 – 1.70 (m, 8H, cyclohexyl), 1.48 (s, 4H, cyclohexyl), 1.28 (d, J=9.9Hz, 3H, cyclohexyl), 1.18 – 1.11 (m, 12H ,-CH (CH
3)
2), 0.89 (dd, J=21.4,11.1Hz, 4H, cyclohexyl), 0.37 (s, 3H, Pd-CH
3).
13CNMR(101MHz,CDCl
3):δ162.47(s),161.98(s),161.48(s),160.99(s),134.81(s),134.44–133.90(m),133.17(d,J＝11.0Hz),132.04(m),131.85(d,J＝21.8Hz),130.94–130.23(m),129.38(s),128.77(dd,J＝30.7,23.7Hz),125.92(s),123.21(s),120.51(s),117.47(s),48.65(s,-CH(CH
3)
2),39.78(s,DMSO),37.90(s,Cy),37.61(s,Cy),35.72(s,Cy),35.45(s,Cy),30.03(s,Cy),29.76(d,J＝50.7Hz,Cy),29.07(s,Cy),27.97(d,J＝6.4Hz,Cy),26.78(dd,J＝25.4,14.2Hz,Cy),25.94(s,Cy),25.63(s,Cy),23.64(s,-CH(CH
3)
2),22.85(s,-CH(CH
3)
2),-1.18(s,Pd-CH
3)。
31PNMR(162MHz,CDCl
3)δ44.44(s),41.45(d,J＝9.5Hz)。
Carry out mass spectroscopy to the compound obtained, result shows, ESI-mass spectrum: (CH
3cN, positively charged ion scans): 618.2228 ([M-DMSO-BAF
-]
+).
Carry out ultimate analysis to the compound obtained, result shows, ultimate analysis calculates C
65h
66bF
24nO
2p
2pdS:C, 50.03; H, 4.26; N, 0.90; Actual C, 50.37; H, 4.16; N, 1.09.
Embodiment 4
The application of catalyzed ethylene polymerization
In glove box, under nitrogen atmosphere, in 350mL autoclave (with magnetic stirring apparatus, oil bath heating unit and thermometer), add the toluene of 20-300mL.Then liquid nitrogen freezing vacuumizes, and is filled with ethene and comes and goes three times, temperature of reaction is adjusted to 20 ~ 100 DEG C, and injects palladium catalyst prepared by a certain amount of embodiment of the present invention or comparative example wherein, makes it be dissolved in solution in 2 milliliters of methylene dichloride.Valve-off, regulates ethylene pressure to be after 9 normal atmosphere, reacts 30 minutes.Stopped reaction, opens reactor, and add methanolic hydrochloric acid (95:5) solution wherein with precipitated solid, filtration under diminished pressure obtains polyethylene crude product, and by pure methanol wash three times, air is dried.Obtain 3 grams of white polyethylenes;
By detecting the poly fusing point obtained, molecular weight, the results are shown in Table 1, the catalyzer that table 1 provides for the embodiment of the present invention and comparative example is the poly the performance test results that obtains of catalyzed ethylene homopolymerization at different conditions.
The catalyzer that table 1 provides for the embodiment of the present invention and comparative example is the poly the performance test results that obtains of catalyzed ethylene homopolymerization at different conditions
Wherein, a is polymerizing condition: 48mL toluene, methylene dichloride 2mL, 9 normal atmosphere.B activity unit 10
5gram every mole per hour.C uses the GPC of universal calibration to measure.D is by dsc, and second time adds heat determination.E adds the AgSbF of 1.2 equivalents
6.F observes the polymkeric substance precipitation shown.G adds the NaBAF of 1.2 equivalents.
The structure of PO-Pd is
Analyzed by the polyethylene adopting the catalyzer in nuclear-magnetism his-and-hers watches 1 described in 4-5 and reaction conditions catalyzed ethylene polymerization to obtain, the results are shown in Figure 2, Fig. 2 is the poly hydrogen spectrum that the embodiment of the present invention prepares, as can be seen from the figure, the poly degree of branching that the present invention prepares is less than 10.
Embodiment 5
The application of catalyzed ethylene and polar monomer copolymerization
In glove box, under nitrogen atmosphere, in 350mL autoclave (with magnetic stirring apparatus, oil bath heating unit and thermometer), add toluene, polar monomer, make overall solution volume be 50 milliliters.And inject catalyzer prepared by a certain amount of embodiment of the present invention and comparative example wherein, make it be dissolved in solution in 5 milliliters of methylene dichloride.Valve-off, regulates ethylene pressure to be after 9 normal atmosphere, passes into ethylene reaction after 1 hour, add methyl alcohol cancellation.The solid of precipitation is obtained by filtration under diminished pressure, then the toluene of heat dissolves, (silicagel column of 200-300 object silica gel is used to be separated by silicagel column while hot, wherein first use the mixture of sherwood oil and methylene dichloride 1:1 as moving phase, re-use pure methylene dichloride and again cross post separation).Collect developping agent, rotary evaporated to dryness.Drain for 40 degree and spend the night.Obtain 0.12 gram of faint yellow solid, be ethylene copolymer;
Detected by the fusing point to the copolymerization product obtained, molecular weight, the results are shown in Table 2, the catalyzer that table 2 provides for the embodiment of the present invention and comparative example is the performance test results of ethylene copolymer that obtains of catalyzed ethylene and polar monomer copolymerization at different conditions.
The catalyzer that table 2 embodiment of the present invention and comparative example provide is the performance test results of ethylene copolymer that obtains of catalyzed ethylene and polar monomer copolymerization at different conditions
Wherein, a polymerizing condition: the cumulative volume of toluene and polar vinyl monomer: 50 milliliters (200 milligrams of 2,6 ditertiary butyl p cresol are in methyl acrylate copoly, 30 microlitres 2,6-di-tert-butyl pyridine is in n-butyl vinyl ether copolymerization), 20 micromole's catalyzer, 1 hour.B is measured by nuclear magnetic resonance spectrometry.C activity is at unit 10
3gram every mole per hour.D uses universal calibration to be measured by GPC.
Polar monomer MA is methyl acrylate, and BE is vinyl n-butyl ether, and AA is allyl acetate.
Analyzed by the ethylene copolymer adopting the catalyzer in nuclear-magnetism his-and-hers watches 2 described in 5-2 and reaction conditions catalyzed ethylene polymerization to obtain, the results are shown in Figure 3, Fig. 3 is the hydrogen spectrum of the ethylene copolymer that the embodiment of the present invention prepares, and as can be seen from the figure, the insertion ratio of MA is 3.2%.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (10)
1. a catalyst ligand, has structure shown in formula (I),
Wherein, R
1be selected from the substituted aryl of C7 ~ C30, the substituting group in described substituted aryl on aryl is the alkoxyl group of C1 ~ C12;
R
2be selected from the substituted aryl of C7 ~ C30, the substituting group in described substituted aryl on aryl is the alkoxyl group of C1 ~ C12;
R
3be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30;
R
4be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30;
R
5be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30.
2. catalyst ligand according to claim 1, is characterized in that, described R
1be selected from the substituted aryl of C9 ~ C18, the substituting group in described substituted aryl on aryl is the alkoxyl group of C3 ~ C8;
R
2be selected from the substituted aryl of C9 ~ C18, the substituting group in described substituted aryl on aryl is the alkoxyl group of C3 ~ C8.
3. catalyst ligand according to claim 1, is characterized in that, described R
3be selected from the alkyl of C3 ~ C12 or the aryl of C8 ~ C20;
R
4be selected from the alkyl of C3 ~ C12 or the aryl of C8 ~ C20;
R
5be selected from the alkyl of C3 ~ C12 or the aryl of C8 ~ C20.
4. preparation method according to claim 1, is characterized in that, described R
1be selected from 2-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-ethoxyl phenenyl, 4-ethoxyl phenenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2-isopropyl phenyl, 4-isopropyl phenyl, 2-octyloxyphenyl, 4-octyloxyphenyl, 2-methoxyl group naphthyl, 2-ethoxynaphthyl, 2-propoxy-naphthyl, 2-isopropoxy naphthyl or 2-octyloxy naphthyl;
R
2be selected from 2-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-ethoxyl phenenyl, 4-ethoxyl phenenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2-isopropyl phenyl, 4-isopropyl phenyl, 2-octyloxyphenyl, 4-octyloxyphenyl, 2-methoxyl group naphthyl, 2-ethoxynaphthyl, 2-propoxy-naphthyl, 2-isopropoxy naphthyl or 2-octyloxy naphthyl.
5. a preparation method for the catalyst ligand described in Claims 1 to 4 any one, comprising:
1) compound shown in the compound shown in formula (I-1) and formula (I-2) is reacted, obtains compound shown in formula (I-3),
Wherein,
R
3be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30,
R
4be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30,
R
5be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30;
2) compound shown in compound and formula (I-4) formula (I-3) Suo Shi is reacted, obtains compound shown in formula (I),
Wherein, R
1be selected from the substituted aryl of C7 ~ C30, the substituting group in the aryl of described replacement on aryl is the alkoxyl group of C1 ~ C12;
R
2be selected from the substituted aryl of C7 ~ C30, the substituting group in the aryl of described replacement on aryl is the alkoxyl group of C1 ~ C12.
6. a catalyzer, comprises part prepared by part described in Claims 1 to 4 any one or preparation method according to claim 5.
7. catalyzer according to claim 6, is characterized in that, described catalyzer is structure shown in formula (II) or the shown structure of formula (III),
Wherein, R
1be selected from the aryl of the replacement of C7 ~ C30, the substituting group in the aryl of described replacement is the alkoxyl group of C1 ~ C12;
R
2be selected from the aryl of the replacement of C7 ~ C30, the substituting group in the aryl of described replacement is the alkoxyl group of C1 ~ C12;
R
3be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30;
R
4be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30;
R
5be selected from the alkyl of C1 ~ C15 or the aryl of C6 ~ C30;
R
6be selected from dimethyl sulfoxide (DMSO), pyridine or 2,5-lutidine;
X is selected from fluorine, chlorine, bromine or iodine;
X
1be selected from four-(3,5-bis-trifluoromethyl) boryl or hexafluoro tellurate radical.
8. a preparation method for the catalyzer described in claim 6 ~ 7 any one, comprising:
Compound formula (I) Suo Shi and Pd precursor compound are reacted, obtains compound shown in formula (II);
By compound formula (II) Suo Shi and NaX
1and R
6shown compound reaction, obtains compound shown in formula (III),
Wherein, R
6be selected from dimethyl sulfoxide (DMSO), pyridine or 2,5-lutidine;
X
1be selected from four-(3,5-bis-trifluoromethyl) boryl or hexafluoro tellurate radical.
9. catalyzer prepared by the catalyzer described in claim 6 ~ 7 any one or preparation method according to claim 8 is as the application of the catalyzer of olefinic polyreaction.
10. application according to claim 9, described olefinic polymerization is alkene homopolymerization or olefin-copolymerization;
Be methyl acrylate, vinyl ether, allyl acetate or chlorallylene with the monomer of olefin-copolymerization in described olefin-copolymerization.
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Cited By (6)
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| CN105384657A (en) * | 2015-12-15 | 2016-03-09 | 中国科学技术大学 | Catalyst ligand, catalyst and preparation methods and application thereof |
| CN108017670A (en) * | 2017-12-15 | 2018-05-11 | 中国科学技术大学 | A kind of compound, palladium compound, nickel compound and preparation method thereof |
| CN109021013A (en) * | 2017-06-08 | 2018-12-18 | 中国科学技术大学 | The phosphono and sulfonic palladium and Raney nickel and its ligand, preparation method and purposes that heterocyclic arene replaces |
| WO2019080877A1 (en) * | 2017-10-24 | 2019-05-02 | 中国石油化工股份有限公司 | Copolymer of olefin and unsaturated carboxylic acid or unsaturated carboxylic acid derivative |
| CN111116810A (en) * | 2018-10-31 | 2020-05-08 | 中国石油化工股份有限公司 | Preparation method of olefin-olefin alcohol copolymer |
| WO2024025605A1 (en) * | 2022-07-27 | 2024-02-01 | University Of Houston System | Nickel catalysts with single alkali ions for homopolymerization and copolymerization |
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| CN105384657A (en) * | 2015-12-15 | 2016-03-09 | 中国科学技术大学 | Catalyst ligand, catalyst and preparation methods and application thereof |
| CN109021013A (en) * | 2017-06-08 | 2018-12-18 | 中国科学技术大学 | The phosphono and sulfonic palladium and Raney nickel and its ligand, preparation method and purposes that heterocyclic arene replaces |
| CN109021013B (en) * | 2017-06-08 | 2020-05-12 | 中国科学技术大学 | Heterocyclic aromatic substituted palladium phosphine sulfonate and nickel catalyst and ligand, preparation method and application thereof |
| WO2019080877A1 (en) * | 2017-10-24 | 2019-05-02 | 中国石油化工股份有限公司 | Copolymer of olefin and unsaturated carboxylic acid or unsaturated carboxylic acid derivative |
| CN108017670A (en) * | 2017-12-15 | 2018-05-11 | 中国科学技术大学 | A kind of compound, palladium compound, nickel compound and preparation method thereof |
| CN108017670B (en) * | 2017-12-15 | 2019-10-25 | 中国科学技术大学 | A kind of compound, palladium compound, nickel compound and preparation method thereof |
| CN111116810A (en) * | 2018-10-31 | 2020-05-08 | 中国石油化工股份有限公司 | Preparation method of olefin-olefin alcohol copolymer |
| WO2024025605A1 (en) * | 2022-07-27 | 2024-02-01 | University Of Houston System | Nickel catalysts with single alkali ions for homopolymerization and copolymerization |
| WO2024025608A1 (en) * | 2022-07-27 | 2024-02-01 | University Of Houston System | Nickel catalysts with two metal cations for homopolymerization and copolymerization |
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