CN115926027B - Supported catalyst and preparation method thereof, and preparation method of polyolefin composite material - Google Patents

Supported catalyst and preparation method thereof, and preparation method of polyolefin composite material Download PDF

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CN115926027B
CN115926027B CN202111120492.4A CN202111120492A CN115926027B CN 115926027 B CN115926027 B CN 115926027B CN 202111120492 A CN202111120492 A CN 202111120492A CN 115926027 B CN115926027 B CN 115926027B
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hydrocarbyl
phenyl
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CN115926027A (en
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陈昶乐
邹陈
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University of Science and Technology of China USTC
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Abstract

The present disclosure provides a supported catalyst, a method of preparing the same, and a method of preparing a polyolefin composite material, the supported catalyst comprising: a metal catalyst and a solid support; wherein the metal catalyst has a first structureThe metal catalyst is attached to the solid carrier; r 1 is selected from the group consisting of hydrocarbyl, nitro, hydroxy, substituted silyl, phenyl, and the like of C 1～C20; r 2 and R 3 are independently selected from hydrogen, C 1～C20 hydrocarbyl, fluoro, chloro, bromo, iodo, nitro, hydroxy, substituted silyl, C 1～C20 substituted hydrocarbyl, phenyl or substituted phenyl; r 4 and R 5 are independently selected from the group consisting of C 1～C20 hydrocarbyl, C 1～C20 substituted hydrocarbyl, phenyl, and substituted phenyl; r 6 and R 7 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C 1～C20 hydrocarbyl, aryl, oxygen-containing group, nitrogen-containing group, sulfur-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, silicon-containing group, or tin-containing group; x is an alkali metal element.

Description

Supported catalyst and preparation method thereof, and preparation method of polyolefin composite material
Technical Field
The disclosure relates to the technical field of catalysts, in particular to a supported catalyst, a preparation method thereof and a preparation method of a polyolefin composite material.
Background
Plastics are one of the highest performance and most cost effective materials available today. The consumer industry relies on the multi-functional properties of plastics. The annual production of synthetic plastics exceeds 3.8 hundred million tons, with polyolefin production accounting for more than half. The design and development of high performance catalysts has received great attention in the academia and industry over the last decades. Despite the huge annual yields of polyolefin materials, one of their biggest drawbacks is their non-polarity, which greatly limits their application in many fields. The polyolefin material is filled and modified by various inorganic and organic fillers, so that the polyolefin composite material is an important way for endowing the polyolefin material with new functions, and is an important source of functional materials required by the current production and living demands of human beings.
At present, polyolefin composite materials are prepared by adopting a method of blending and modifying polyolefin materials by adopting inorganic and organic fillers, and the method is simple and convenient to operate, but has the problems of easy precipitation of the blend, uneven filler distribution, damage to the mechanical properties of structural materials and the like. In the field of composite material research, in order to solve the problems, the following methods are adopted to improve, such as modifying the filler, increasing the contact surface and the viscosity of the filler and the polymer substrate, carrying out organic structure grafting on the surface of the inorganic filler, and increasing the compatibility of the filler and the polymer substrate; carrying out grafting modification on the nonpolar polymer base material, improving the polarity, and increasing the compatibility of the nonpolar polymer base material and the polar filler so as to improve the blending effect; adding a small amount of interfacial compatilizer to increase the compatibility between the polymer substrate and the filler.
Disclosure of Invention
First, the technical problem to be solved
Aiming at the prior art problems, the present disclosure provides a supported catalyst, a preparation method thereof and a preparation method of polyolefin composite material, which are used for at least partially solving the technical problems.
(II) technical scheme
The present disclosure provides a supported catalyst comprising a metal catalyst and a solid support, wherein the metal catalyst has a first structureThe metal catalyst is attached to the solid carrier; r 1 is selected from the group consisting of hydrocarbyl of C 1～C20, nitro, hydroxy, substituted silicon-based, substituted hydrocarbyl of C 1～C20, phenyl, or substituted phenyl; r 2 and R 3 are independently selected from hydrogen, C 1～C20 hydrocarbyl, fluoro, chloro, bromo, iodo, nitro, hydroxy, substituted silyl, C 1～C20 substituted hydrocarbyl, phenyl or substituted phenyl; r 4 and R 5 are independently selected from the group consisting of C 1～C20 hydrocarbyl, C 1～C20 substituted hydrocarbyl, phenyl, and substituted phenyl; r 6 and R 7 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C 1～C20 hydrocarbyl, aryl, oxygen-containing group, nitrogen-containing group, sulfur-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, silicon-containing group, or tin-containing group; x is an alkali metal element.
Optionally, the R 2、R3 moieties are bonded to each other to form a ring; and/or, the R 4、R5 moieties are bonded to each other to form a ring; and/or the R 6、R7 moieties are bonded to each other to form a ring.
Alternatively, R 1 is selected from the group consisting of hydrocarbyl of C 1～C6, hydroxy, substituted silyl, substituted hydrocarbyl of C 1～C6, phenyl, pentafluorophenyl, or substituted phenyl; r 2 and R 3 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C 1～C6 hydrocarbyl, hydroxy, C 1～C6 substituted hydrocarbyl; r 4 and R 5 are independently selected from the group consisting of C 1～C6 hydrocarbyl, C 1～C6 substituted hydrocarbyl, phenyl, and substituted phenyl; r 6 and R 7 are independently selected from hydrogen, chlorine, bromine, C 1～C6 hydrocarbyl, aryl, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, boron-containing groups, aluminum-containing groups, phosphorus-containing groups, or silicon-containing groups; x is any one of lithium, sodium or potassium.
Optionally, the solid support is selected from one or more of silica, magnesia, titania, zinc oxide, alumina, magnesium chloride, glass fiber, graphene, expanded graphite, ammonium polyphosphate or carbon black.
Another aspect of the present disclosure provides a method for preparing a supported catalyst, comprising: preparing a ligand solution and a metal source nickel solution respectively; dropwise adding the ligand solution into a metal source nickel solution, and reacting to obtain a compound I-H; adding a metal source X to react with a compound I-H to obtain a metal catalyst; adding a metal catalyst into a first organic solvent dispersed with a solid carrier, and reacting to obtain a supported catalyst; wherein the ligand has a second structureCompounds I-H have a third structureThe metal catalyst has a first structureR 1 is selected from the group consisting of hydrocarbyl of C 1～C20, nitro, hydroxy, substituted silicon-based, substituted hydrocarbyl of C 1～C20, phenyl, or substituted phenyl; r 2 and R 3 are independently selected from hydrogen, C 1～C20 hydrocarbyl, fluoro, chloro, bromo, iodo, nitro, hydroxy, substituted silyl, C 1～C20 substituted hydrocarbyl, phenyl or substituted phenyl; r 4 and R 5 are independently selected from the group consisting of C 1～C20 hydrocarbyl, C 1～C20 substituted hydrocarbyl, phenyl, and substituted phenyl; r 6 and R 7 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C 1～C20 hydrocarbyl, aryl, oxygen-containing group, nitrogen-containing group, sulfur-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, silicon-containing group, or tin-containing group; the metal source X is an alkali metal hydride.
Optionally, preparing a solution of the ligand comprises: reacting the compound a with dihydropyran to obtain a compound a-1; reacting the compound a-1 with butyl alkali metal, and adding the compound b to obtain a dihydropyran protection structure of the ligand; adding hydrochloric acid to remove the protecting group to obtain a ligand; wherein the compound a has a fourth structureCompound a-1 has a fifth structureCompound b has a sixth structure
Optionally, the mass ratio of the metal catalyst to the solid carrier is 1/50000-1/20; the first organic solvent is selected from one or more of tetrahydrofuran, petroleum ether, toluene, benzene, methylene dichloride, tetrachloromethane, 1, 4-dioxane or 1, 2-dichloroethane.
Alternatively, a metal source nickel solution containing Ni (COD) 2、Py2NiMe2 or (DME) NiBr 2 is prepared.
Another aspect of the present disclosure provides a method of preparing a polyolefin composite, catalyzed by the supported catalyst of any one of the embodiments of the present disclosure; wherein the olefin comprises ethylene or a-olefin, the a-olefin being a terminal olefin of C 3～C18, the a-olefin comprising propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, 1-decene, 1-dodecene, 1-octadecene, and mixtures thereof; the supported catalyst acts as a filler for the composite material in situ after the polymerization reaction; processes employed to polymerize olefins include slurry polymerization, loop polymerization, or gas phase polymerization; the preparation of the polyolefin composite is carried out in a second organic solvent comprising hydrocarbons of less than 12 carbons, cyclic hydrocarbons, aromatic hydrocarbons or substituted aromatic hydrocarbons and mixtures thereof; the preparation temperature of the polyolefin composite material is 0-200 ℃ and the pressure is 0.1-50 MPa.
Alternatively, an electrically conductive, thermally conductive, flame retardant or photodegradable composite material is prepared.
(III) beneficial effects
The present disclosure provides a supported catalyst, wherein OX groups are introduced at para positions of metal centers of metal complexes, and by introducing metal ions such as lithium, sodium, potassium, etc. to interact with a solid carrier, the interaction is formed by intermolecular interaction forces between the metal ions and surface hydroxyl groups of an inorganic solid carrier or an organic structure of an organic solid carrier, so that an adhesion effect of the metal catalyst on the carrier is further improved, and a metal active center of the catalyst is controllably exposed, so that the metal active center can be coordinated with olefin to form polyolefin, a loading capacity of a post-transition metal nickel catalyst is provided, and a high-performance and multifunctional polyolefin composite material can be prepared by the supported post-transition metal catalyst with high activity.
The present disclosure provides a method for in situ preparation of polyolefin composites with late transition metal catalysts, providing a new route for the preparation of functional composites. The content of carrier filler in the composite material can be regulated and controlled by one-step polymerization, and the prepared polyolefin composite material has excellent mechanical properties. Different carriers can be replaced based on one metal catalyst, so that a high-performance material with electric conductivity, heat conductivity, flame retardance and photodegradation performance can be prepared easily, and the high-performance material has certain universality.
Drawings
The above and other objects, features and advantages of the present disclosure will become more apparent from the following description of embodiments thereof with reference to the accompanying drawings in which:
FIG. 1 schematically illustrates a flow chart of a supported catalyst preparation method according to an embodiment of the present disclosure;
FIG. 2 schematically illustrates a graph of mechanical properties of a polyolefin composite according to an embodiment of the disclosure;
fig. 3 schematically illustrates a polymer molecular weight variation graph of a polyolefin composite according to an embodiment of the disclosure.
Detailed Description
For the purposes of promoting an understanding of the principles and advantages of the disclosure, reference will now be made to the embodiments illustrated in the drawings and specific language will be used to describe the same.
In the drawings or description, like or identical parts are provided with the same reference numerals. Features of the embodiments illustrated in the description may be combined freely to form new solutions without conflict, in addition, each claim may be used alone as one embodiment or features of the claims may be combined as a new embodiment, and in the drawings, the shape or thickness of the embodiments may be enlarged and labeled in a simplified or convenient manner. Furthermore, elements or implementations not shown or described in the drawings are of a form known to those of ordinary skill in the art. Additionally, although examples of parameters including particular values may be provided herein, it should be appreciated that the parameters need not be exactly equal to the corresponding values, but may be approximated to the corresponding values within acceptable error margins or design constraints.
The various embodiments of the disclosure described above may be freely combined to form additional embodiments, unless otherwise technical hurdles or contradictions exist, which are all within the scope of the disclosure.
Although the present disclosure has been described with reference to the accompanying drawings, the examples disclosed in the drawings are intended to illustrate preferred embodiments of the present disclosure and are not to be construed as limiting the present disclosure. The dimensional proportions in the drawings are illustrative only and should not be construed as limiting the present disclosure.
Although a few embodiments of the present general inventive concept have been shown and described, it would be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the general inventive concept, the scope of which is defined in the claims and their equivalents.
According to an embodiment of the present disclosure, there is provided a supported catalyst having the structure of formula (I),
Wherein the structure of formula (I) comprises a metal catalyst (I') and a solid support, the metal catalyst being attached to the solid support; r 1 is selected, for example, from the group consisting of C 1～C20 hydrocarbyl, nitro, hydroxy, substituted silicon-based, C 1～C20 substituted hydrocarbyl, phenyl, or substituted phenyl. r 2 and R 3 are independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, C 1～C20 hydrocarbyl, nitro, hydroxy, substituted silyl, C 1～C20 substituted hydrocarbyl, The phenyl or substituted phenyl groups, the R 2、R3 moieties may be bonded to each other to form a ring. R 4 and R 5 are independently selected from the group consisting of C 1～C20 hydrocarbyl, C 1～C20 substituted hydrocarbyl, phenyl, and substituted phenyl, The R 4、R5 moieties may be bonded to each other to form a ring. r 6 and R 7 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C 1～C20 hydrocarbyl, aryl, oxygen-containing groups, nitrogen-containing groups (e.g., pyridine, etc.), sulfur-containing groups (e.g., dimethyl sulfide, dimethyl sulfoxide, etc.), boron-containing groups (e.g., tris (pentafluorophenyl) borane, etc.), and, the R 6、R7 moieties may be bonded to each other to form a ring, an aluminum-containing group (e.g., triethylaluminum, triisobutylaluminum, etc.), a phosphorus-containing group (e.g., tri-t-butylphosphine, triphenylphosphine, etc.), a silicon-containing group (e.g., trimethoxysilyl, triethoxysilyl, etc.), or a tin-containing group. x may be lithium, sodium, potassium, etc. The material of the carrier is solid inorganic matters or solid organic matters. The substitution patterns in the "substituted silicon group", "substituted hydrocarbon group", "substituted phenyl group" in the present disclosure may be, for example, halogen substitution, hydroxyl substitution, ester substitution, carboxyl substitution, nitro substitution, and the like. "bonding to form a ring" in this disclosure means bonding or forming a ring, or bonding and forming a ring simultaneously.
Further, R 1 is selected from, for example, a hydrocarbyl group of C 1～C6, a hydroxyl group, a substituted silyl group, a substituted hydrocarbyl group of C 1～C6, a phenyl group or a substituted phenyl group, a pentafluorophenyl group. r 2 and R 3 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C 1～C6 hydrocarbyl, hydroxy, C 1～C6 substituted hydrocarbyl, The R 2、R3 moieties may be bonded to each other to form a ring. r 4 and R 5 are independently selected from the group consisting of C 1～C6 hydrocarbyl, C 1～C6 substituted hydrocarbyl, phenyl, and substituted phenyl, The R 4、R5 moieties may be bonded to each other to form a ring. R 6 and R 7 are independently selected from hydrogen, chlorine, bromine, C 1～C6 hydrocarbyl, aryl, oxygen-containing groups, nitrogen-containing groups (e.g., pyridine, etc.), sulfur-containing groups (e.g., dimethylsulfide, dimethylsulfoxide, etc.), boron-containing groups (e.g., tris (pentafluorophenyl) borane, etc.), and combinations of, The R 6、R7 moieties may be bonded to each other to form a ring, including an aluminum-containing group (e.g., triethylaluminum, triisobutylaluminum, etc.), a phosphorus-containing group (e.g., tri-t-butylphosphine, triphenylphosphine, etc.), or a silicon-containing group (e.g., trimethoxysilyl, triethoxysilyl, etc.). X may be lithium, sodium, potassium, etc. The carrier is selected from one or more of solid inorganic matters or organic matters such as silicon dioxide, magnesium oxide, titanium dioxide, zinc oxide, aluminum oxide, magnesium chloride, glass fiber, graphene, expanded graphite, ammonium polyphosphate, carbon black and the like.
Preferably, the catalyst having the structure of formula (I) has, for example, the structure of formula (I 1-Na-Al2O3), wherein formula (I 1) may be replaced with the structure of formula (I 2), formula (I 3), formula (I 4), or the like, and Na may be replaced with Li or K.
Wherein the metal catalyst in the structure of formula (I) has the structure of formula (I 1), formula (I 2), formula (I 3) or formula (I 4), for example.
Fig. 1 schematically shows a flow chart of a supported catalyst preparation method according to an embodiment of the present disclosure.
According to an embodiment of the present disclosure, as shown in fig. 1, a preparation method of a supported catalyst includes, for example:
s110, preparing a ligand solution and a metal source nickel solution respectively.
According to an embodiment of the present disclosure, a ligand having the structure of formula (II) and a metal source nickel (e.g., ni (COD) 2、Py2NiMe2、(DME)NiBr2, etc.) are respectively dissolved in an organic solvent, e.g., toluene, for example, under an argon or nitrogen atmosphere.
S120, adding the ligand solution into the metal source nickel solution dropwise, and reacting to obtain the compound I-H.
According to embodiments of the present disclosure, the ligand solution is added dropwise to the metal source nickel solution, reacted at room temperature, for example, for 1 to 12 hours, and then filtered, and the solvent is removed to obtain the compound I-H.
S130, adding a metal source X to react with the compound I-H to obtain the metal catalyst.
According to the embodiment of the disclosure, the compound I-H reacts with metal sources X (such as lithium hydride, sodium hydride, potassium hydride and the like) of lithium, sodium, potassium and the like to obtain the metal catalyst, and the structure is shown as the formula (I-X).
And S140, adding the metal catalyst into the first organic solvent with the carrier dispersed therein, and reacting to obtain the supported catalyst.
According to the embodiment of the disclosure, a certain amount of metal catalyst is taken and added into an organic solvent in which a carrier is dispersed, and the catalyst is stirred for 1 to 120 minutes, filtered and pumped to obtain the supported catalyst shown in the formula (I). The mass ratio of the metal catalyst to the carrier is, for example, 1 to 20 to 50000. The organic solvent of the carrier is, for example, one or more selected from tetrahydrofuran, petroleum ether, toluene, benzene, methylene chloride, tetrachloromethane, 1, 4-dioxane and 1, 2-dichloroethane. The structural change of the related compound in the chemical reaction is shown as a reaction formula:
Wherein the ligand has the structure of formula (II), R1 is selected from, for example, C 1～C20 hydrocarbyl, nitro, hydroxy, substituted silyl, C 1～C20 substituted hydrocarbyl, phenyl, or substituted phenyl; r 2 and R 3 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C 1～C20 hydrocarbyl, nitro, hydroxy, substituted silicon, C 1～C20 substituted hydrocarbyl, phenyl or substituted phenyl. The R 2、R3 moieties may be bonded to each other to form a ring. R 4 and R 5 are independently selected from the group consisting of C 1～C20 hydrocarbyl, C 1～C20 substituted hydrocarbyl, phenyl, and substituted phenyl, and the R 4、R５ moieties may be bonded to each other to form a ring.
Further, R 1 is selected from, for example, a hydrocarbyl group of C 1～C6, a hydroxyl group, a substituted silyl group, a substituted hydrocarbyl group of C 1～C6, a phenyl group or a substituted phenyl group, a pentafluorophenyl group. R 2 and R 3 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C 1～C6 hydrocarbyl, hydroxy, C 1～C6 substituted hydrocarbyl, and the R 2、R3 moieties may form a ring with each other. R 4 and R 5 are independently selected from the group consisting of C 1～C6 hydrocarbyl, C 1～C6 substituted hydrocarbyl, phenyl, and substituted phenyl, and the R 4、R5 moieties may be bonded to each other to form a ring.
According to embodiments of the present disclosure, a ligand having a structure of formula (II) may be prepared by, for example, reacting a compound a with dihydropyran under nitrogen or argon to obtain a product a-1, reacting the product a-1 with butyllithium, adding a compound b to the reaction system to prepare a dihydropyran protecting structure of the ligand, and adding hydrochloric acid to release the protecting group to obtain a ligand having a structure of formula (II).
Preferably, the ligand having the structure of formula (II) has the structure of formula (II 1), formula (II 2), formula (II 3) or formula (II 4), for example.
For a further understanding of the present disclosure, the preparation of the catalyst provided by the present disclosure is described in detail below in connection with specific examples, and the scope of the present disclosure is not limited by the following examples.
The following examples illustrate the details of the present disclosure, and the data presented include ligand synthesis, catalyst synthesis, ethylene polymerization or copolymerization processes, wherein the catalyst synthesis is performed in the absence of water and oxygen, all sensitive materials are stored in a glove box, all solvents are strictly dried to remove water, ethylene gas is purified by a water removal deoxygenation column, and all supports are dried. Methyl acrylate is purified by a dehydration, deoxygenation and reduced pressure distillation method. All materials are commercially available, unless otherwise specified.
According to embodiments of the present disclosure, a silica gel column, such as with 200-300 mesh silica gel, and a nuclear magnetic column, such as with a Bruker 400MHz nuclear magnetic instrument. Elemental analysis is measured, for example, by the university of science and technology center of China. The molecular weight and molecular weight distribution are determined, for example, by GPC (polystyrene columns, HR2 and HR4, tank temperature 45 ℃, using Water 1515 and Water 2414 pumps. Mobile phase tetrahydrofuran, flow rate 1.0 ml per minute, using polydisperse polystyrene as standard). Mass spectrometry is determined, for example, using Thermo LTQ Orbitrap XL (ESI+) or P-SIMS-Gly of Bruker Daltonics Inc (EI+). Single crystal X-ray diffraction analysis, e.g. using Oxford Diffraction Gemini S Ultra CCD single crystal diffractometer, cu K alphaAnd (5) radiating at room temperature.
Example 1:
Preparation of 2- (tert-butyl) -6- ((2 ',6' -dimethoxy- [1,1' -biphenyl ] -2-yl) (phenyl) phosphino) benzene-1, 4-diol.
According to the examples of the present disclosure, for example, tert-butylhydroquinone (50 mmol) and dihydropyran are reacted with stirring at room temperature for 12 hours to give a product having a tetrahydropyran protecting group, which is dissolved in 200mL of tetrahydrofuran, placed at 0℃and n-BuLi (55 mmol) is dropwise added thereto, after 2 hours of reaction, chloro (2 ',6' -dimethoxy- [1,1 '-biphenyl ] -2-yl) (phenyl) phosphine (50 mmol) is added thereto, the reaction is slowly warmed to room temperature, continued for 12 hours, quenched with water, the organic phase is extracted with diethyl ether, the obtained organic phase is concentrated to 100mL, deoxygenated by freezing cycle, 15mL of concentrated hydrochloric acid is added under nitrogen atmosphere, reacted for 6 hours, neutralized with NaHCO 3 aqueous solution, quenched with water, the organic phase is extracted with diethyl ether, dried over anhydrous MgSO 4, filtered, concentrated, and flash column chromatography gives a white solid, namely 2- (tert-butyl) -6- ((2', 6 '-dimethoxy- [1,1' -biphenyl ] -2-yl) (phenyl) phosphino) benzene-1, 4-diol .1H NMR(400MHz,CDCl3)δ7.41(dd,J＝7.5,1.5Hz,1H),7.29-7.24(m,5H),7.24-7.16(m,4H)6.76(d,J＝3.0Hz,1H),6.51(dd,J＝8.3,4.3Hz,2H),6.24(dd,J＝4.2,3.0Hz,1H),6.16(d,J＝10.5Hz,1H),4.41(s,1H),3.51(s,3H),3.45(s,3H),1.32(s,9H).13C NMR(101MHz,CDCl3)δ157.75,157.71,152.29,152.15,148.32,141.42,141.21,137.48,135.97,133.66,133.54,133.49,131.14,131.10,129.60,129.55,128.46,128.33,128.29,127.65,122.03,118.57,117.37,116.43,103.92,103.82,55.66,55.46,34.93,29.55.31P NMR(162MHz,CDCl3)δ-37.22.ESI-MS(m/z)：[M+H]+ Calcd for C30H32O4P,487.20327;Found：487.20386.
Example 2:
preparation of 2- (bis (2-methoxyphenyl) phosphono) -6- (tert-butyl) benzene-1, 4-diol.
According to the examples of the present disclosure, the synthetic method of 2- (bis (2-methoxyphenyl) phosphono) -6- (tert-butyl) benzene-1, 4-diol is different from example 1 in that: for example, 50mmol of chlorobis (2-methoxyphenyl) phosphine is used in place of chlorobis (2 ',6' -dimethoxy- [1,1' -biphenyl ] -2-yl) (phenyl) phosphine to obtain 2- (bis (2-methoxyphenyl) phosphono) -6- (tert-butyl) benzene-1, 4-diol having the structure of formula (II 2) .1H NMR(400MHz,CDCl3)δ7.28-7.19(m,2H),6.82-6.70(m,7H),6.52(d,J＝10.8Hz,1H),6.13(dd,J＝4.8,3.0Hz,1H),4.37(s,1H),3.61(s,6H),1.30(s,9H).13C NMR(101MHz,CDCl3)δ160.12,159.97,151.78,151.58,147.18,147.15,136.35,136.33,132.23,129.42,121.75,120.05,120.04,119.51,116.72,116.69,115.63,109.39,109.36,54.66,33.89,33.87,28.37.31P NMR(162MHz,CDCl3)δ-51.31.ESI-MS(m/z)：[M+H]+Calcd for C24H26O4P,409.16125;Found：409.20351.
Example 3:
Preparation of 3- ((2 ',6' -dimethoxy- [1,1 '-biphenyl ] -2-yl) (phenyl) phosphino) - [1,1' -biphenyl ] -2, 5-diol.
According to the examples of the present disclosure, for example, 2, 5-dihydroxybiphenyl (50 mmol) was reacted with dihydropyran at room temperature with stirring for 12 hours to give a product with a tetrahydropyran protecting group, which was dissolved in 200mL of tetrahydrofuran, placed at 0℃and n-BuLi (55 mmol) was added dropwise, after 2 hours of reaction, chloro (2 ',6' -dimethoxy- [1,1' -biphenyl ] -2-yl) (phenyl) phosphine (50 mmol) was added, slowly warmed to room temperature, the reaction was continued for 12 hours, quenched with water, the organic phase was extracted with diethyl ether, the resulting organic phase was concentrated to 100mL, chilled for deoxygenation, 15mL of concentrated hydrochloric acid was added under nitrogen atmosphere, reacted for 6 hours, neutralized with aqueous NaHCO 3, quenched with water, the organic phase was extracted with diethyl ether, dried over anhydrous MgSO 4, filtered, concentrated, flash column chromatography afforded a white solid, 3- ((2 ',6' -dimethoxy- [1,1' -biphenyl ] -2, 5-diol) - [1,1' -biphenyl ] -2-diol .1H NMR(400MHz,CDCl3)δ7.42-7.33(m,5H),7.31-7.23(m,3H),7.23-7.18(m,4H),7.18-7.14(m,4H),6.69(d,J＝5.6Hz,1H),6.53-6.48(m,1H),6.47-6.41(m,2H),5.67(s,1H),4.70(s,1H),3.51(s,3H),3.36(s,3H).13C NMR(101MHz,CDCl3)δ156.83,156.51,156.50,151.80,151.61,144.91,144.89,140.68,140.35,135.90,134.10,132.67,132.65,132.46,130.02,129.96,129.41,128.58,128.39,128.05,127.85,127.40,127,31,127.24,126.85,126.74,119.32,119.29,117.84,117.76,115.51,115.49,102.91,102.70,76.32,76.20,76.00,75.68,54.59,54.45,28.67,13.10.31P NMR(162MHz,CDCl3)δ-35.27.ESI-MS(m/z)：[M+H]+Calcd for C32H26O4P,505.16512;Found：505.14115.
Example 4:
Preparation of 3- ((2 ',6' -dimethoxy- [1,1' -biphenyl ] -2-yl) (phenyl) phosphino) -2',3',4',5',6' -pentafluoro- [1,1' -biphenyl ] -2, 5-diol.
According to embodiments of the present disclosure, the synthetic methods of 3- ((2 ',6' -dimethoxy- [1,1' -biphenyl ] -2-yl) (phenyl) phosphino) -2',3',4',5',6' -pentafluoro- [1,1' -biphenyl ] -2, 5-diol differ from embodiment 3 by, for example: substitution of 2, 5-dihydroxybiphenyl with 2',3',4',5',6' -pentafluoro- [1,1' -biphenyl ] -2, 5-diol gives 3- ((2 ',6' -dimethoxy- [1,1' -biphenyl ] -2-yl) (phenyl) phosphino) -2',3',4',5',6' -pentafluoro- [1,1' -biphenyl ] -2, 5-diol having the structure of formula (II 4) .1H NMR(400MHz,CDCl3)δ7.49-7.42(m,5H),7.39-7.24(m,5H),6.73-6.66(m,5H),6.69(s,1H),6.55(d,J＝8.1Hz,1H),5.21(s,1H),3.89(s,3H),3.76(s,3H).13C NMR(101MHz,CDCl3)δ157.49,156.22,155.97,145.04,143.10,137.58,136.82,135.59,135.47,134.11,132.94,131.45,129.76,129.14,128.92,128.65,128.61,128.56,125.59,120.93,119.24,117.94,114.15,106.11,56.25,53.21.31P NMR(162MHz,CDCl3)δ-17.77.19F NMR(472MHz,CDCl3)δ-140.79,-149.99,-159.54.ESI-MS(m/z)：[M+H]+ Calcd for C32H21F5O4P,504.51103;Found：504.41701.
Example 5:
preparation of the Supported catalyst (I 1-Na-Al2O3).
According to the embodiment of the disclosure, for example, ligand (II 1) (1.0 mmol) and metallic nickel source (Py 2NiMe2) (1.1 mmol) are respectively dissolved in toluene under nitrogen atmosphere, the ligand solution is dripped into the metallic nickel source (Py 2NiMe2) solution, stirred, reacted for 1h at room temperature, filtered to obtain a brown yellow solution, sodium hydride (1.1 mmol) is continuously added, and the solvent is removed in vacuum to obtain complex (I 1 -Na), 10mg of complex (I 1 -Na) is taken, added into toluene solution dispersed with 1g of aluminum oxide carrier, stirred for 30 min, filtered, leached to obtain solid, and dried to obtain the supported catalyst (I 1-Na-Al2O3).
Example 6:
Preparation of the Supported catalyst (I 1 -Na-graphene).
According to an embodiment of the present disclosure, the synthesis method of the supported catalyst (I 1 -Na-graphene) is different from that of embodiment 5 in that: for example, 5g of graphene is substituted for 1g of aluminum oxide to obtain a supported catalyst having the formula (I 1 -Na-graphene).
Example 7:
Preparation of the Supported catalyst (I 1 -Na-APP).
According to an embodiment of the present disclosure, the method for synthesizing the supported catalyst (I 1 -Na-ammonium polyphosphate) differs from that of embodiment 5 in that: for example, 5g of ammonium polyphosphate (APP) are substituted for 1g of aluminum oxide, giving a supported catalyst having the formula (I 1 -Na-ammonium polyphosphate).
Example 8:
Preparation of the Supported catalyst (I 1-Na-TiO2).
According to an embodiment of the present disclosure, the synthesis method of the supported catalyst (I 1-Na-TiO2) differs from that of embodiment 5 in that: for example, 1g of titanium dioxide is substituted for 1g of aluminum oxide to give a supported catalyst having the formula (I 1-Na-TiO2).
Example 9:
Preparation of the Supported catalyst (I 1 -Na-ZnO).
According to the examples of the present disclosure, the synthesis method of the supported catalyst (I 1 -Na-ZnO) is different from example 5 in that: for example, 1g of zinc oxide is substituted for 1g of aluminum oxide to obtain a supported catalyst having the formula (I 1 -Na-ZnO).
Example 10:
preparation of Supported catalyst (I 1 -Na-GF).
According to the examples of the present disclosure, the synthesis method of the supported catalyst (I 1 -Na-GF) is different from example 5 in that: for example, 5g of Glass Fiber (GF) was used in place of 1g of aluminum oxide to obtain a supported catalyst having the formula (I 1 -Na-GF).
Example 11:
Preparation of the Supported catalyst (I 1-Na-SiO2).
According to an embodiment of the present disclosure, the synthesis method of the supported catalyst (I 1-Na-SiO2) differs from that of embodiment 5 in that: for example, 1g of silica is substituted for 1g of alumina to obtain a supported catalyst having the formula (I 1-Na-SiO2).
Example 12:
Preparation of the Supported catalyst (I 1-K-Al2O3).
According to an embodiment of the present disclosure, the synthesis method of the supported catalyst (I 1-K-Al2O3) differs from that of embodiment 5 in that: for example, potassium hydride (1.1 mmol) is taken in place of sodium hydride (1.1 mmol) to give a supported catalyst having formula (I 1-K-Al2O3).
Example 13:
Preparation of the Supported catalyst (I 1 -K-ammonium polyphosphate).
According to an embodiment of the present disclosure, the synthesis method of the supported catalyst (I 1-K-Al2O3) differs from that of embodiment 5 in that: for example, potassium hydride (1.1 mmol) was used in place of sodium hydride (1.1 mmol), and 5g of ammonium polyphosphate was used in place of 1g of aluminum oxide to obtain a supported catalyst having the formula (I 1 -K-ammonium polyphosphate).
The present disclosure also provides an application of the supported catalytic olefin polymerization in preparing polyolefin composites in situ, for example comprising: the supported catalyst of the structure of formula (I) is used for catalyzing olefin polymerization to prepare polyolefin composite materials in situ. Wherein the olefin includes ethylene, a-olefin, etc., and a-olefin refers to a terminal olefin of C 3～C18, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, 1-decene, 1-dodecene, 1-octadecene, mixtures thereof, etc. The polymerization may be, for example, slurry polymerization, loop polymerization, gas phase polymerization or other forms of polymerization processes. The polymerization is generally carried out in an organic solvent, for example hydrocarbons, cyclic hydrocarbons or aromatic hydrocarbons. To facilitate reactor operation and polymerization of the product, the organic solvent may use hydrocarbons of less than 12 carbons, such as but not limited to hexane, toluene, chlorobenzene, and mixtures thereof. The polymerization temperature is maintained, for example, at 0℃to 200 ℃. The polymerization pressure may vary from 0.1 to 50 MPa.
Methods of preparing polyolefin composites according to embodiments of the present disclosure may be used, for example, to prepare electrically conductive, thermally conductive, flame retardant, or degradable materials.
The present disclosure illustrates, for example, by examples 14-19, methods and composite properties for catalytically preparing polyolefin composites using supported catalysts having the above-described structure.
Example 14
According to the embodiments of the present disclosure, the supported catalysts prepared in embodiments 5 to 13 are used to catalyze ethylene polymerization to prepare polyolefin composite materials, and specific polymerization methods are as follows: in a glove box, and under nitrogen atmosphere, 90mL of n-heptane was added to a 350mL autoclave (with a magnetic stirring device, an oil bath heating device, and a thermometer), then the vessel was connected to a high-pressure line and evacuated to a tube, and the vessel temperature was set at 80 ℃ and kept for 5 minutes. The supported catalysts (containing 1 umol) prepared in examples 5 to 13 were dispersed in 10mL of n-heptane and injected into the autoclave through a syringe. Then, an ethylene valve was opened, ethylene was introduced into the autoclave, and the ethylene pressure was adjusted to 8 atm, and the reaction was carried out for 10 minutes. And stopping the reaction, opening the autoclave, adding ethanol to precipitate solid, filtering under reduced pressure, and drying in a vacuum drying oven to obtain white solid.
The results of preparing polyolefin composites by catalyzing ethylene polymerization using the catalysts prepared in examples 5 to 13 are shown in table 1:
TABLE 1
Wherein a polymerization conditions are, for example: n-heptane=100 mL, ethylene=8 atmospheres, polymerization temperature 80 degrees celsius; b The melting point is determined, for example, by means of a differential scanning calorimeter. c Weight average molecular weight=10 4g·mol-1, molecular weight measurement is carried out, for example, by GPC with polystyrene as standard trichlorobenzene as solvent at 150 ℃.
Example 15
Fig. 2 schematically illustrates a graph of mechanical properties of a polyolefin composite according to an embodiment of the disclosure.
Mechanical property testing of polyolefin composites prepared using items 1,4, 5, 7 and 8 in example 14 according to the examples of the present disclosure: for example, the obtained multifunctional polar polyolefin metal complex material was made into dumbbell-shaped bars (length 25 mm. Width 2mm. Thickness 0.4 mm), and the mechanical properties were tested by a universal tester (UTM 2502), and the results were shown in the stress-strain curve of fig. 2.
As can be seen from fig. 2, the supported catalyst in the present disclosure can catalyze ethylene polymerization to prepare a polyolefin composite material under a certain condition, the tensile strength of the prepared polyolefin composite material can reach 45MPa, and the elongation at break can reach 1500%.
Example 16
Thermal conductivity testing of polyolefin composites prepared according to item 1 of example 14 and commercial HDPE blanks (commercial polyethylene (exkesen mobil, MPE 2018 HA)) according to examples of the present disclosure: for example, the resulting polyolefin composite and commercial HDPE blanks were each formed into a circular sheet (25 mm diameter by 0.5mm thickness) and tested for thermal conductivity by a laser thermal conductivity meter (Netzsch LFA 467) at 30 degrees celsius, which showed a thermal diffusivity of 0.38mm 2/S, while the commercial HDPE blanks had a thermal diffusivity of 0.24mm 2/S.
From the test results, the polyolefin composite material prepared in the item 1 in the embodiment 14 has a certain heat conduction property, and is obviously better than a commercial HDPE blank, which shows that the polyolefin composite material prepared by the method can obviously improve the heat conduction property of the polyethylene polyolefin composite material when the inorganic matter content is lower.
Example 17
Flame retardant performance test of polyolefin composites and commercial HDPE blanks prepared using item 3 in example 14 according to the examples of the present disclosure: for example, the resulting polyolefin composite and commercial HDPE blanks were each formed into square sheets (100 mm x 3 mm), and flammability tests were performed on a cone calorimeter (FTT, UK) according to ISO 5660 standard procedure by means of a cone calorimeter, each sample being wrapped in aluminum foil and horizontally exposed to an external heat flux of 35kW/m 2. The flame retardant property test results are shown in table 2,
TABLE 2
As can be seen from the results in Table 2, the supported catalyst prepared by using ammonium polyphosphate as the metal complex carrier catalyzes the one-step in-situ synthesis of ethylene to produce polyolefin composite material containing about 10% ammonium polyphosphate, which has better flame retardant performance parameters than commercial HDPE. The polyolefin composite material prepared by the method has certain flame retardant property.
Example 18
According to an example of the present disclosure, the conductivity test of the polyolefin composite material and commercial HDPE blanks prepared in application example 1, item 2, was used: for example, the resulting polyolefin composite and commercial HDPE blanks were each formed into a circular sheet (25 mm diameter by 0.5mm thickness) and tested for electrical conductivity at 30 degrees celsius by a digital multimeter (DELIXI ELECTRIC) and the electrical conductivities were calculated from the measured resistances as shown in table 3.
TABLE 3 Table 3
From the results in table 3, it can be seen that the conductivity of the polyolefin composite material containing about 9.2% graphene, which is prepared by using graphene as a metal complex carrier and is prepared by using a catalyst for catalyzing ethylene one-step in-situ synthesis, is 1.9x10 6 times that of commercial HDPE, and is significantly better than commercial HDPE. The polyolefin composite material prepared by the method has certain conductive performance.
Example 19
Fig. 3 schematically illustrates a polymer molecular weight variation graph of a polyolefin composite according to an embodiment of the disclosure.
According to the examples of the present disclosure, the photodegradation performance test of the polyolefin composite material prepared in application example 1 item 4 was adopted: for example, the resulting polyolefin composite was formed into a circular film (diameter 25 x thickness 0.1 mm), and the photodegradation properties of the composite film were studied by exposing the sample to ultraviolet light under irradiation of an ultraviolet lamp (350-400 nm, irradiance=40 w/M 2, test chamber temperature=35 ℃), the results of which can be represented by changes in the molecular weight of the polymer, as shown in fig. 3, M N represents the number average molecular weight, and M W represents the weight average molecular weight.
As can be seen from fig. 3, after irradiating the composite film with ultraviolet rays for 0 hours, 48 hours, 96 hours, and 192 hours, the number average molecular weight of the polymer component thereof is significantly reduced, and the molecular weight distribution is increased, indicating that the polyolefin composite material has photodegradation performance.
In summary, the embodiment of the disclosure provides a supported catalyst, by introducing an OX group at the para position of the metal center of the metal complex, introducing metal ions such as lithium, sodium, potassium and the like to interact with a carrier, the loading effect of the metal catalyst is improved, the metal active center of the catalyst is controllably exposed, so that the catalyst can coordinate with olefin and insert into the olefin to generate polyolefin, the loading capacity of the post-transition metal nickel catalyst is provided, and the high-activity preparation of the high-performance and multifunctional polyolefin composite material of the supported post-transition metal catalyst can be realized. By changing different carriers, the high-performance material with electric conductivity, heat conductivity, flame retardance and photodegradation performance is prepared easily.
The product embodiment is similar to the method embodiment in that details are not fully omitted, please refer to the method embodiment, and the details are not repeated here.
It should be understood that the specific order or hierarchy of steps in the processes disclosed are examples of exemplary approaches. Based on design preferences, it is understood that the specific order or hierarchy of steps in the processes may be rearranged without departing from the scope of the present disclosure. The accompanying method claims present elements of the various steps in a sample order, and are not meant to be limited to the specific order or hierarchy.
It should be further noted that the directional terms mentioned in the embodiments, such as "upper", "lower", "front", "rear", "left", "right", etc., are only with reference to the directions of the drawings, and are not intended to limit the scope of the present disclosure. Like elements are denoted by like or similar reference numerals throughout the drawings. Conventional structures or constructions will be omitted when they may obscure the understanding of this disclosure. And the shape, size and position relation of each component in the figure do not reflect the actual size, proportion and actual position relation.
In the foregoing detailed description, various features are grouped together in a single embodiment for the purpose of streamlining the disclosure. This method of disclosure is not to be interpreted as reflecting an intention that the claimed embodiments of the subject matter require more features than are expressly recited in each claim. Rather, as the following claims reflect, the present disclosure is directed to less than all of the features of a single disclosed embodiment. Thus, the following claims are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate preferred embodiment of this disclosure.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present disclosure, the meaning of "a plurality" is at least two, such as two, three, etc., unless explicitly specified otherwise. As used in the specification or claims, the term "comprising" is intended to be inclusive in a manner similar to the term "comprising" as "comprising," as "comprising" is interpreted when employed as a transitional word in a claim. Any use of the term "or" in the specification of the claims is intended to mean "non-exclusive or".
While the foregoing embodiments have been described in some detail for purposes of clarity of understanding, it will be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and that any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the present disclosure are intended to be included within the scope of the present disclosure.

Claims (10)

1.A supported catalyst, comprising: a metal catalyst and a solid support;
wherein the metal catalyst has a first structure The metal catalyst is attached to the solid support;
r 1 is selected from the group consisting of C 1~C20 hydrocarbyl, C 1~C20 substituted hydrocarbyl, phenyl, or substituted phenyl;
r 2 and R 3 are independently taken from hydrogen;
R 4 and R 5 are independently selected from phenyl or substituted phenyl;
R 6 is taken from the hydrocarbon group of C 1~C20 and R 7 is taken from a nitrogen-containing group;
X is an alkali metal element.
2. The supported catalyst of claim 1, wherein the R 2、R3 moieties are bonded to each other to form a ring; and/or the number of the groups of groups,
The R 4、R5 moieties are bonded to each other to form a ring; and/or the number of the groups of groups,
The R 6、R7 moieties are bonded to each other to form a ring.
3. The supported catalyst of claim 1, wherein R 1 is selected from the group consisting of hydrocarbyl of C 1~C6, substituted hydrocarbyl of C 1~C6;
r 2 and R 3 are independently taken from hydrogen;
R 6 is a hydrocarbyl group taken from C 1~C6;
X is any one of lithium, sodium or potassium.
4. The supported catalyst of claim 1, wherein the solid support is selected from one or more of silica, magnesia, titania, zinc oxide, aluminum oxide, magnesium chloride, glass fiber, graphene, expanded graphite, ammonium polyphosphate, or carbon black.
5. A method for preparing a supported catalyst, comprising:
preparing a ligand solution and a metal source nickel solution respectively;
dropwise adding the ligand solution into the metal source nickel solution, and reacting to obtain a compound I-H;
adding a metal source X to react with the compound I-H to obtain a metal catalyst;
Adding the metal catalyst into a first organic solvent dispersed with a solid carrier, and reacting to obtain the supported catalyst;
wherein the ligand has a second structure The compound I-H has a third structureThe metal catalyst has a first structure；
R 1 is selected from the group consisting of C 1~C20 hydrocarbyl, C 1~C20 substituted hydrocarbyl, phenyl, or substituted phenyl;
r 2 and R 3 are independently taken from hydrogen;
R 4 and R 5 are independently selected from phenyl or substituted phenyl;
R 6 is taken from the hydrocarbon group of C 1~C20 and R 7 is taken from a nitrogen-containing group;
the metal source X is an alkali metal hydride.
6. The method for preparing a metal catalyst according to claim 5, wherein preparing a solution of the ligand comprises:
Reacting the compound a with dihydropyran to obtain a compound a-1;
Reacting the compound a-1 with butyl alkali metal, and adding a compound b to obtain a dihydropyran protection structure of the ligand;
Adding hydrochloric acid to remove a protecting group to obtain the ligand;
Wherein the compound a has a fourth structure The compound a-1 has a fifth structureThe compound b has a sixth structure。
7. The method for preparing a metal catalyst according to claim 5, wherein the mass ratio of the metal catalyst to the solid carrier is 1/50000-1/20;
The first organic solvent is selected from one or more of tetrahydrofuran, petroleum ether, toluene, benzene, methylene dichloride, tetrachloromethane, 1, 4-dioxane or 1, 2-dichloroethane.
8. The method for producing a metal catalyst according to claim 5, wherein a metal source nickel solution containing Ni (COD) 2、Py2NiMe2 or (DME) NiBr 2 is produced.
9. A process for the preparation of a polyolefin composite, characterized in that it is catalyzed by a supported catalyst according to any one of claims 1 to 4;
Wherein the olefin comprises ethylene or an alpha-olefin, which is a terminal olefin of C 3~C18;
the supported catalyst acts as a filler for the composite material in situ after polymerization;
Processes employed to polymerize olefins include slurry polymerization, loop polymerization, or gas phase polymerization;
The preparation of the polyolefin composite is carried out in a second organic solvent comprising hydrocarbons of less than 12 carbons, substituted aromatic hydrocarbons and mixtures thereof;
The preparation temperature of the polyolefin composite material is 0-200 ℃, and the pressure is 0.1-50 MPa.
10. The method of preparing a polyolefin composite according to claim 9, wherein the composite is prepared to be electrically, thermally, flame or photodegradable.
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