CN103483482A - Functional isotactic polypropylene and preparation method thereof - Google Patents
Functional isotactic polypropylene and preparation method thereof Download PDFInfo
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Abstract
The invention provides functional isotactic polypropylene and a preparation method thereof. The functional isotactic polypropylene is prepared through polymerizing polymerization monomers including propylene and terminal-halogenated 1-olefin under the action of a catalyst and a catalyst promoter, wherein the catalyst is a dimethyl pyridine amine-hafnium complex, and the catalyst promoter is triphenylmethyl tetrakis-(pentafluorophenyl)-borate. The catalytic systems of the catalyst and the catalyst promoter have high three-dimensional regioselectivity for the polymerization monomers and have excellent copolymerization capacity for long-chain halogenated 1-olefin, so that the prepared functional isotactic polypropylene has relatively high regularity and high isotacticity ([mmmm]) of over 99%.
Description
Technical field
The present invention relates to the polypropylene technology field, relate in particular to a kind of functional isotatic polypropylene and preparation method thereof.
Background technology
Polypropylene is a kind of thermoplastic resin made by propylene polymerization, presses the methyl arrangement position, and polypropylene can be divided into isotatic polypropylene, Atactic Polypropelene and syndiotactic polypropylene.The same side that methyl is arranged in molecular backbone chain claims isotatic polypropylene; If being arranged in the both sides of molecular backbone chain out of orderly, methyl claims Atactic Polypropelene; The both sides that are arranged alternately in molecular backbone chain when methyl become syndiotactic polypropylene.Isotatic polypropylene be most widely used in the world at present, one of resin that increase of production is the fastest.With other thermoplastic resins, compare, the characteristics such as it has low density, high-melting-point, source is wide, price is low and mechanical property is superior, chemical stability is good, polypropylene has developed into one of packing, light industry, building, electronics, electrical equipment, the indispensable basic raw material of automobile and other industries in recent years.
Compared to isotatic polypropylene, the performance of functional isotatic polypropylene is more excellent.For example, isotactic directional property copolymerization by propylene and ω-halogen-alpha-olefin obtains contains the functional isotatic polypropylene that hangs halogen group, when retaining excellent physical and mechanical properties, can improve the nonpolar defect of polypropylene, effectively the wetting ability of Reinforced Polypropylene, colourability, static resistance and with the performances such as the consistency of polar macromolecule material and clinging power, improve its added value.Contain the multipolymer that hangs halogen group and there is active reaction site, can pass through the reaction of class click chemistry, easily and efficiently halogen group is converted into to other various polarity group, thereby obtain diversified functional isotatic polypropylene material.
From the sixties in last century so far, numerous research groups adopt heterogeneous Ziegler-Natta catalyst or catalyzed by homogeneous metallocene catalyst to carry out the copolymerization of propylene and ω-halogen-alpha-olefin.For example, Bacskai etc. adopts TiCl
3/ Et
2the AlCl catalyst system carries out the copolymerization of propylene and multiple ω-halogen-alpha-olefin, and in the gained multipolymer, the high-content of halogen group reaches the 7wt%(polymer science, Polym.Sci., Part A1965,3,2491).But Ziegler-Natta catalyst gained copolymer structure is indefinite, molecular weight and polar group skewness, and is difficult to guarantee high degree of isotacticity.Recently, Kashiwa research group is used Et (Ind)
2zrCl
2the catalysis of/MAO system the copolymerization of propylene and the bromo-1-undecylene of 11-, in the gained multipolymer, the content of bromine group is between 1.5～10.3mol%, molecular weight is at 11.2～19.6kgmol
-1between (polymkeric substance circular, Polym.Bull.2007,59,177).Although in metallocene catalysis system gained multipolymer, it is very high that the content of halogen group can reach, and the molecular weight of polymkeric substance is less than 20kgmol
-1, and eliminate owing to containing by different way structural unit and β-hydrogen or halogen of inserting two keys that reaction produces, the molecular chain structure irregularity of polymkeric substance, melt temperature are lower.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of polymer molecular chain compound with regular structure, melt temperature is higher, molecular weight is high functional isotatic polypropylene and preparation method thereof.
In view of this, the invention provides a kind of functional isotatic polypropylene, comprise the repeating unit with formula I structure and the repeating unit with formula II structure;
Wherein, x is halogen;
Y is 1～16;
The side chain of described functional isotatic polypropylene is at homonymy.
Preferably, the described repeating unit with formula II structure is greater than zero and be less than or equal to 11.7mol% in the insertion rate of described functional isotatic polypropylene.
The present invention also provides the preparation method of described functional isotatic polypropylene, comprising:
Under the effect of catalyzer and promotor, propylene and the haloolefin with formula III structure are carried out to polymerization in inert solvent, obtain functional isotatic polypropylene; Described catalyzer is the lutidine amine hafnium complexes with formula IV structure, and described promotor is triphen carbon four (pentafluorophenyl group) borate;
Wherein, x is halogen;
Y is 1～16;
R
1, R
2with R
3be selected from independently of one another the different alkyl of hydrogen or C1～C10.
Preferably, described lutidine amine hafnium complexes and the boratory mol ratio of described triphen carbon four (pentafluorophenyl group) are 1:(1～4).
Preferably, the temperature of described polymerization is 0～100 ℃, and the time of described polymerization is 10～60min.
Preferably, described inert solvent is hydro carbons, cyclic hydrocar-bons or aromatic hydrocarbons.
Preferably, described lutidine amine hafnium complexes is 1:(300～1500 with the mol ratio with haloolefin of formula III structure).
Preferably, also comprise pickling agent in the process of described polymerization, described pickling agent is alkylaluminium cpd.
Preferably, the mol ratio of described lutidine amine hafnium complexes and described alkylaluminium cpd is 1:(50～400).
The invention provides a kind of preparation method of functional isotatic polypropylene, in the process of the functional isotatic polypropylene of preparation, it is lutidine amine hafnium complexes that the present invention adopts catalyzer, promotor is the boratory catalyst system catalyzing propone of triphen carbon four (pentafluorophenyl group) when having the haloolefin polymerization of formula III structure, three-dimensional, regioselectivity is high, and halo 1-alkene is had to fabulous copolymerized ability, tolerance to some haloolefin is better, does not have β-side reactions such as hydrogen or halogen elimination; Compared to ziegler-natta catalyzed system and luxuriant zirconium catalyst system, the remarkable superior part of this catalyst system is to obtain the polymkeric substance of high molecular high isotactic by the high reactivity polypropylene, and the halo 1-alkene of long-chain is had to fabulous copolymerized ability.Experimental result shows, has the insertion rate of repeating unit of formula II structure in the present invention for being greater than zero and be less than or equal to 11.7mol%, and the melt temperature of functional isotatic polypropylene is 82～155 ℃, and weight-average molecular weight is 66～144kgmol
-1.
The accompanying drawing explanation
The functional isotatic polypropylene that Fig. 1 is the embodiment of the present invention 1 preparation
13c NMR spectrogram;
The functional isotatic polypropylene that Fig. 2 is the embodiment of the present invention 1 preparation
1h NMR spectrogram;
The typical gel permeation chromatography graphic representation that Fig. 3 is the functional isotatic polypropylene for preparing of the present invention;
The typical differential thermal analysis curve figure that Fig. 4 is the functional isotatic polypropylene for preparing of the present invention.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The embodiment of the invention discloses a kind of functional isotatic polypropylene, comprise the repeated structural unit with formula I structure and the repeated structural unit with formula II structure;
Wherein, x is halogen;
Y is 1～16;
The side chain of described functional isotatic polypropylene is at homonymy.
In described functional isotatic polypropylene, described x is preferably Cl, Br and I, and described y is the number with methylene radical in the repeating unit of formula II structure, is preferably 8～16.
According to the present invention, the degree of isotacticity of described functional isotatic polypropylene approaches 100%, and weight-average molecular weight is 66.0～144kg/mol, and molecular weight distributing index is 1.81～2.65, and melt temperature is adjustable between 82～155 ℃; The described insertion rate of repeating unit in described isotatic polypropylene with formula II structure is greater than zero and be less than or equal to 11.7mol%.
In the present invention, described functional isotatic polypropylene wherein a part of segment can have formula (V)～formula (XI) structure:
The present invention also provides the preparation method of described functional isotatic polypropylene, comprising:
Under the effect of catalyzer and promotor, propylene and the haloolefin with formula III structure are carried out to polymerization in inert solvent, obtain functional isotatic polypropylene; Described catalyzer is the lutidine amine hafnium complexes with formula IV structure, and described promotor is triphen carbon four (pentafluorophenyl group) borate;
Wherein, x is halogen;
Y is 1～16.
R
1, R
2with R
3be selected from independently of one another the different alkyl of hydrogen or C1～C10.
The present invention is in the process of the functional isotatic polypropylene of preparation, adopting catalyzer is that lutidine amine hafnium complexes and promotor are that triphen carbon four (pentafluorophenyl group) borate catalyst system catalyzing propone is the 1-olefinic polymerization of end halo with the alkene with formula III structure, thereby makes functional isotatic polypropylene.
In the process of the described functional isotatic polypropylene of preparation, all compounds to moisture and oxygen sensitivity are all in the MBraun glove box or utilize standard Schlenk technology to carry out under nitrogen protection.
According to the present invention, the R in described lutidine amine hafnium complexes
1, R
2with R
3be preferably independently of one another hydrogen, methyl, sec.-propyl or the tertiary butyl.Described lutidine amine hafnium complexes and the boratory mol ratio of described triphen carbon four (pentafluorophenyl group) are preferably 1:(1～4), 1:(2～3 more preferably); The mol ratio of the 1-alkene of described catalyzer and described end halo is preferably 1:(300～1500), 1:(700～1400 more preferably).
Of the present invention being aggregated in inert solvent carried out, and adopts the method for solution polymerization to carry out polymerization; Described inert solvent is preferably hydro carbons, cyclic hydrocar-bons or aromatic hydrocarbons, more preferably toluene.The temperature of described polymerization is preferably 0～100 ℃, and more preferably 25～75 ℃, the time of described polymerization is preferably 10～60min, more preferably 20～40min.The present invention is in polymerization process, also added pickling agent, described pickling agent is preferably alkylaluminium cpd, more preferably triisobutyl aluminium, the impurity of described alkylaluminium cpd in can the cleaning reaction system in polymerization process, also can adjust the molecular weight of multipolymer simultaneously.The mol ratio of described lutidine amine hafnium complexes and described triisobutyl aluminium is preferably 1:(50～400), 1:(100～300 more preferably); Most preferably be 1:(150～250).
Concrete reaction conditions and step prepared by described functional isotatic polypropylene are as follows:
Under propylene atmosphere, add successively dry toluene in dry polymerization reactor, the 1-alkene of end halo and the toluene solution of triisobutyl aluminium, stir 10～20min under design temperature after, add the mixture initiation reaction (total liquor capacity is 40mL) of catalyzer and promotor, continuing to pass into propylene and keeping propylene pressure is 1 normal atmosphere, after reacting 10～30min, reaction solution is poured into containing 10%(V/V) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer.Product that filtration obtains adopts after washing with acetone 3 times puts into dry 24～36h under 60～80 ℃ of vacuum drying ovens, obtains functional isotatic polypropylene.
The preparation of functional isotatic polypropylene described in the present invention can be carried out according to following reaction formula:
In the process that the application is detected at the functional isotatic polypropylene to preparation, adopt NMR (Nuclear Magnetic Resonance) spectrum to measure the molecular structure of multipolymer; Adopt differential thermal analysis to measure the melt temperature of polymkeric substance; Adopt the molecular weight and molecular weight distribution index of gel permeation chromatography polymkeric substance.Wherein, NMR (Nuclear Magnetic Resonance) spectrum refers to polymkeric substance
1h and
13c NMR spectrum is measured under 120 ℃ by Varian Unity-400 type nuclear magnetic resonance spectrometer, and TMS is interior mark, and deuterium is solvent for orthodichlorobenzene.The insertion rate of ω in multipolymer-iodo-α-undecylene is used
1h NMR spectrum analysis calculates: IUDmol%=[6I
3.12-3.27ppm/ (2I
0.90-2.07ppm-13I
3.12-3.27ppm)] * 100%, I
xrepresentative is at the integral area at place, xppm peak, and the insertion rate of other polar monomer calculates according to similar method.Differential thermal analysis (DSC) refers to the melt temperature (T of polymkeric substance
m) by Perkin-ElmerPyris1 DSC differential scanning calorimeter, measured, temperature rate is 10 ℃/min, rescan.Gel permeation chromatography (GPC) refers to that the molecular weight and molecualr weight distribution index of polymkeric substance measured by PLGPC-220 type gel permeation chromatograph; Adopt the RI-Laser detector, three chromatographic columns that packed column is Plgel10 μ m MIXED-BLS, solvent is 1,2,4-trichlorobenzene (TCB), and added 2 of 0.05wt%, 6-di-tert-butyl-4-methy phenol (BHT) is made oxidation inhibitor, probe temperature is 150 ℃, and flow velocity is 1.0mL/min, and adopting PL EasiCal PS-1 is standard specimen.
The application is in the process of the functional isotatic polypropylene of preparation, and selecting lutidine amine hafnium complexes is catalyzer and triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) be promotor, compared to ziegler-natta catalyzed system and luxuriant zirconium catalyst system, the remarkable superior part of this catalyst system is to obtain the polymkeric substance of high molecular high isotactic by the high reactivity polypropylene, and the 1-alkene of long-chain is had to fabulous copolymerized ability.Under the effect of the catalyzer of copolymerized ability excellence, by the 1-olefin-copolymerization of propylene and halo, obtained the high molecular high isotactic that structure is clear and definite ([mmmm] > 99%) containing the functional isotatic polypropylene that enriches halogen group.The weight-average molecular weight of functional isotatic polypropylene is 66.0～144kg/mol, and molecular weight distributing index (PDI) is 1.81～2.65.The insertion rate of polar monomer can be greater than zero and be less than or equal between 11.7mol% and regulate, and the melt temperature of multipolymer can be regulated between 82～155 ℃.
With the functional isotatic polypropylene of the halogen-containing group of bibliographical information, compare, the prepared functional isotatic polypropylene of the present invention is when guaranteeing high polar group content, the regularity of molecular weight and molecular chain structure significantly improves, this is during due to the 1-olefinic polymerization of selected catalyst system catalyzing propone and end halo, three-dimensional, regioselectivity is high, and the halo 1-alkene to long-chain has fabulous copolymerized ability, better to the tolerance of some haloolefin, does not have β-side reactions such as hydrogen or halogen elimination.Experimental result shows, when the content of polar monomer is 11.7mol%, the weight-average molecular weight of polymkeric substance is 130kg/mol, and molecular weight distributing index is 1.81; And bibliographical information result relatively preferably: when the content of polar monomer is 10.3mol%, the weight-average molecular weight of polymkeric substance is 11.2kg/mol, and molecular weight distributing index is 1.84.
In order further to understand the present invention, below in conjunction with embodiment, the preparation method of functional isotatic polypropylene provided by the invention is elaborated, protection scope of the present invention is not limited by the following examples.
In following examples, the anhydrous and oxygen-free solvent such as toluene is made by MBraun SPS solvent purification treatment system; The method preparation that the pyridine amine hafnium complexes reference literature (macromole, Macromolecules2007,40,3510) adopted is described, other raw materials are commercially available prod.
Under propylene atmosphere, add successively the 30mL dry toluene in dry polymerization reactor, the iodo-1-undecylene of 7.4mmol11-and 1.0mL pickling agent triisobutyl aluminium (Al (
ibu)
3) toluene solution (0.5M), stir 10min at 25 ℃ of temperature after, add 5 μ mol catalyzer lutidine amine hafnium complexes (R
1, R
2with R
3be all sec.-propyl) and 10 μ mol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) the mixture initiation reaction, total liquor capacity is 40mL, continuing to pass into propylene and keeping propylene pressure is 1 normal atmosphere, after reaction 10min, reaction solution is poured into containing 10%(V/V) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer; The product that filtration obtains to be to put into dry 24h under 60 ℃ of vacuum drying ovens after washing with acetone 3 times, the 0.32g polymkeric substance of weighing to obtain, and the catalytic activity of polymkeric substance is 3.80 * 10
5g/mol
hfh, weight-average molecular weight is 134kg/mol relatively, the relative molecular weight dispersion index is 1.97, by
1the insertion rate that H NMR spectrum elucidation calculates the iodo-1-undecylene of 11-is 11.7mol%, and the DSC test shows that the melt temperature of this sample is 82 ℃.As shown in Figure 1, Fig. 1 is the iodo-1-undecylene of propylene/11-multipolymer
13c NMR spectrogram; As shown in Figure 2, the iodo-1-undecylene of the propylene/11-multipolymer that Fig. 2 is the embodiment of the present invention 1 preparation
1h NMR spectrogram; As shown in Figure 4, the typical DSC graphic representation that Fig. 4 is the functional isotatic polypropylene for preparing of the present invention, the DSC curve of the iodo-1-undecylene of the propylene/11-multipolymer that in figure, curve c is embodiment 1 preparation, the DSC curve that curve a is isotatic polypropylene.
Under propylene atmosphere, add successively the 30mL dry toluene in dry polymerization reactor, the iodo-1-undecylene of 3.7mmol11-and 1.0mL Al (
ibu)
3toluene solution (0.5M), stir 10min at 25 ℃ of temperature after, add 5 μ mol catalyzer lutidine amine hafnium complexes (R
1, R
2with R
3be all sec.-propyl) and 10 μ mol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) the mixture initiation reaction, total liquor capacity is 40mL, continuing to pass into propylene and keeping propylene pressure is 1 normal atmosphere, after reaction 10min, reaction solution is poured into containing 10%(V/V) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer; The product that filtration obtains to be to put into dry 24h under 60 ℃ of vacuum drying ovens after washing with acetone 3 times, the 0.5g polymkeric substance of weighing to obtain, and the catalytic activity of polymkeric substance is 6.00 * 10
5g/mol
hfh, weight-average molecular weight is 130kg/mol relatively, the relative molecular weight dispersion index is 1.81, by
1the insertion rate that H NMR spectrum elucidation calculates the iodo-1-undecylene of 11-is 7.50mol%, and the DSC test shows that the melt temperature of this sample is 105 ℃.As described in Figure 3, the GPC graphic representation that Fig. 3 is the functional isotatic polypropylene for preparing of the present invention, in figure, a is the GPC graphic representation of the iodo-1-undecylene of the propylene/11-multipolymer for the embodiment of the present invention 2 preparations; The typical DSC graphic representation that Fig. 4 is the functional isotatic polypropylene for preparing of the present invention, the DSC curve of the iodo-1-undecylene of the propylene/11-multipolymer that in figure, curve b is embodiment 2 preparations.
Under propylene atmosphere, add successively the 30mL dry toluene in dry polymerization reactor, the iodo-1-undecylene of 1.5mmol11-and 1.0mL Al (
ibu)
3toluene solution (0.5M), stir 10min at 25 ℃ of temperature after, add 5 μ mol catalyzer lutidine amine hafnium complexes (R
1, R
2with R
3be all sec.-propyl) and 10 μ mol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) the mixture initiation reaction, total liquor capacity is 40mL, continuing to pass into propylene and keeping propylene pressure is 1 normal atmosphere, after reaction 10min, reaction solution is poured into containing 10%(V/V) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer; Product that filtration obtains adopts after washing with acetone 3 times puts into dry 24h under 60 ℃ of vacuum drying ovens, the 0.72g polymkeric substance of weighing to obtain, and the catalytic activity of polymkeric substance is 8.60 * 10
5g/mol
hfh, weight-average molecular weight is 144kg/mol relatively, the relative molecular weight dispersion index is 2.03, by
1the insertion rate that H NMR spectrum elucidation calculates the iodo-1-undecylene of 11-is 3.00mol%, and the DSC test shows that the melt temperature of this sample is 127 ℃.
Under propylene atmosphere, add successively the 30mL dry toluene in dry polymerization reactor, the iodo-1-undecylene of 3.7mmol11-and 1.5mL Al (
ibu)
3toluene solution (0.5M), at 25 ℃ of temperature, stir after 10 minutes, add 5 μ mol catalyzer lutidine amine hafnium complexes (R
1, R
2with R
3be all sec.-propyl) and 10 μ mol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) the mixture initiation reaction, total liquor capacity is 40mL, continuing to pass into propylene and keeping propylene pressure is 1 normal atmosphere, after reaction 10min, reaction solution is poured into containing 10%(V/V) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer.The product that filtration obtains to be to put into dry 24h under 60 ℃ of vacuum drying ovens after washing with acetone 3 times, the 0.54g polymkeric substance of weighing to obtain, and catalytic activity is 6.50 * 10
5g/mol
hfh, weight-average molecular weight is 101kg/mol relatively, the relative molecular weight dispersion index is 2.45, by
1the insertion rate that H NMR spectrum elucidation calculates the iodo-1-undecylene of 11-is 7.00mol%, and the DSC test shows that the melt temperature of this sample is 108 ℃.As described in Figure 3, the typical GPC graphic representation that Fig. 3 is the functional isotatic polypropylene for preparing of the present invention, the GPC graphic representation of the iodo-1-undecylene of the propylene/11-multipolymer that in figure, b is the embodiment of the present invention 4 preparations.
Under propylene atmosphere, add successively the 30mL dry toluene in dry polymerization reactor, the iodo-1-undecylene of 3.7mmol11-and 2.0mL Al (
ibu)
3toluene solution (0.5M), stir 10min at 25 ℃ of temperature after, add 5 μ mol catalyzer lutidine amine hafnium complexes (R
1, R
2with R
3be all sec.-propyl) and 10 μ mol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) the mixture initiation reaction, total liquor capacity is 40mL, continuing to pass into propylene and keeping propylene pressure is 1 normal atmosphere, after reaction 10min, reaction solution is poured into containing 10%(V/V) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer; The product that filtration obtains to be to put into dry 24h under 60 ℃ of vacuum drying ovens after washing with acetone 3 times, the 0.35g polymkeric substance of weighing to obtain, and the catalytic activity of polymkeric substance is 4.20 * 10
5g/mol
hfh, weight-average molecular weight is 66kg/mol relatively, the relative molecular weight dispersion index is 2.65, by
1the insertion rate that H NMR spectrum elucidation calculates the iodo-1-undecylene of 11-is 7.20mol%, and the DSC test shows that the melt temperature of this sample is 101 ℃.As described in Figure 3, the typical GPC graphic representation that Fig. 3 is the functional isotatic polypropylene for preparing of the present invention, the GPC graphic representation of the iodo-1-undecylene of the propylene/11-multipolymer that in figure, c is the embodiment of the present invention 5 preparations.
Under propylene atmosphere, add successively the 30mL dry toluene in dry polymerization reactor, the iodo-1-butylene of 3.7mmol4-and 1.0mL Al (
ibu)
3toluene solution (0.5M), stir 10min at 25 ℃ of temperature after, add 5 μ mol catalyzer lutidine amine hafnium complexes (R
1, R
2for sec.-propyl, R
3for hydrogen) and 10 μ mol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) the mixture initiation reaction, total liquor capacity is 40mL, continuing to pass into propylene and keeping propylene pressure is 1 normal atmosphere, after reaction 10min, reaction solution is poured into containing 10%(V/V) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer; The product that filtration obtains to be to put into dry 24h under 60 ℃ of vacuum drying ovens after washing with acetone 3 times, the 0.10g polymkeric substance of weighing to obtain, and the catalytic activity of polymkeric substance is 1.20 * 10
5g/mol
hfh, weight-average molecular weight is 80.0kg/mol relatively, the relative molecular weight dispersion index is 2.32, by
1the insertion rate that H NMR spectrum elucidation calculates the iodo-1-butylene of 4-is 1.80mol%, and the DSC test shows that the melt temperature of this sample is 135 ℃.
Under propylene atmosphere, add successively the 30mL dry toluene in dry polymerization reactor, the bromo-1-undecylene of 3.7mmol11-and 1.0mL Al (
ibu)
3toluene solution (0.5M), stir 10min at 25 ℃ of temperature after, add 5 μ mol catalyzer lutidine amine hafnium complexes (R
1, R
2for sec.-propyl, R
3for hydrogen) and 10 μ mol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) the mixture initiation reaction, total liquor capacity is 40mL, continuing to pass into propylene and keeping propylene pressure is 1 normal atmosphere, after reaction 10min, reaction solution is poured into containing 10%(V/V) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer; The product that filtration obtains to be to put into dry 24h under 60 ℃ of vacuum drying ovens after washing with acetone 3 times, the 0.09g polymkeric substance of weighing to obtain, and the catalytic activity of polymkeric substance is 1.10 * 10
5g/mol
hfh, weight-average molecular weight is 121kg/mol relatively, the relative molecular weight dispersion index is 2.10, by
1the insertion rate that H NMR spectrum elucidation calculates the bromo-1-undecylene of 11-is 3.40mol%, and the DSC test shows that the melt temperature of this sample is 119 ℃.
Under propylene atmosphere, add successively the 30mL dry toluene in dry polymerization reactor, the chloro-1-undecylene of 3.7mmol11-and 1.0mL Al (
ibu)
3toluene solution (0.5M), stir 10min at 25 ℃ of temperature after, add 5 μ mol catalyzer lutidine amine hafnium complexes (R
1, R
2for sec.-propyl, R
3for hydrogen) and 10 μ mol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) the mixture initiation reaction, total liquor capacity is 40mL, continuing to pass into propylene and keeping propylene pressure is 1 normal atmosphere, after reaction 10min, reaction solution is poured into containing 10%(V/V) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer; The product that filtration obtains to be to put into dry 24h under 60 ℃ of vacuum drying ovens after washing with acetone 3 times, the 0.04g polymkeric substance of weighing to obtain, and the catalytic activity of polymkeric substance is 0.50 * 10
5g/mol
hfh, weight-average molecular weight is 108kg/mol relatively, the relative molecular weight dispersion index is 2.97, by
1the insertion rate that H NMR spectrum elucidation calculates the chloro-1-undecylene of 11-is 3.00mol%, and the DSC test shows that the melt temperature of this sample is 119 ℃.
Embodiment 9
Under propylene atmosphere, add successively the 30mL dry toluene in dry polymerization reactor, iodo-1-19 carbenes of 3.7mmol19-and 1.0mL Al (
ibu)
3toluene solution (0.5M), stir 10min at 25 ℃ of temperature after, add 5 μ mol catalyzer lutidine amine hafnium complexes (R
1, R
2for the tertiary butyl, R
3for hydrogen) and 10 μ mol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) the mixture initiation reaction, total liquor capacity is 40mL, continuing to pass into propylene and keeping propylene pressure is 1 normal atmosphere, after reaction 10min, reaction solution is poured into containing 10%(V/V) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer; The product that filtration obtains to be to put into dry 24h under 60 ℃ of vacuum drying ovens after washing with acetone 3 times, the 0.6g polymkeric substance of weighing to obtain, and the catalytic activity of polymkeric substance is 7.20 * 10
5g/mol
hfh, weight-average molecular weight is 145kg/mol relatively, the relative molecular weight dispersion index is 2.07, by
1the insertion rate that H NMR spectrum elucidation calculates iodo-1-19 carbenes of 19-is 8.50mol%, and the DSC test shows that the melt temperature of this sample is 102 ℃.
Under propylene atmosphere, add successively the 30mL dry toluene in dry polymerization reactor, bromo-1-19 carbenes of 3.7mmol19-and 1.0mL Al (
ibu)
3toluene solution (0.5M), stir 10min at 25 ℃ of temperature after, add 5 μ mol catalyzer lutidine amine hafnium complexes (R
1, R
2for the tertiary butyl, R
3for hydrogen) and 10 μ mol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) the mixture initiation reaction, total liquor capacity is 40mL, continuing to pass into propylene and keeping propylene pressure is 1 normal atmosphere, after reaction 10min, reaction solution is poured into containing 10%(V/V) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer.The product that filtration obtains to be to put into dry 24h under 60 ℃ of vacuum drying ovens after washing with acetone 3 times, the 0.3g polymkeric substance of weighing to obtain, and the catalytic activity of polymkeric substance is 3.60 * 10
5g/mol
hfh, weight-average molecular weight is 105kg/mol relatively, the relative molecular weight dispersion index is 1.96, by
1the insertion rate that H NMR spectrum elucidation calculates bromo-1-19 carbenes of 19-is 5.40mol%, and the DSC test shows that the melt temperature of this sample is 112 ℃.
Under propylene atmosphere, add successively the 30mL dry toluene in dry polymerization reactor, chloro-1-19 carbenes of 3.7mmol19-and 1.0mL Al (
ibu)
3toluene solution (0.5M), at 25 ℃ of temperature, stir after 10 minutes, add 5 μ mol catalyzer lutidine amine hafnium complexes (R
1, R
2for the tertiary butyl, R
3for hydrogen) and 10 μ mol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) the mixture initiation reaction, total liquor capacity is 40mL, continuing to pass into propylene and keeping propylene pressure is 1 normal atmosphere, after reacting 10 minutes, reaction solution is poured into containing 10%(V/V) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer; The product that filtration obtains to be to put into after washing with acetone 3 times under 60 ℃ of vacuum drying ovens dry 24 hours, the 0.2g polymkeric substance of weighing to obtain, and the catalytic activity of polymkeric substance is 2.40 * 10
5g/mol
hfh, weight-average molecular weight is 102kg/mol relatively, the relative molecular weight dispersion index is 1.97, by
1the insertion rate that the HNMR spectrum elucidation calculates chloro-1-19 carbenes of 19-is 4.90mol%, and the DSC test shows that the melt temperature of this sample is 114 ℃.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.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 improvement and modification also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, make professional and technical personnel in the field can realize or use the present invention.Multiple modification to these embodiment will be apparent for those skilled in the art, and General Principle as defined herein can be in the situation that do not break away from the spirit or scope of the present invention, realization in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (9)
1. a functional isotatic polypropylene, comprise the repeating unit with formula I structure and the repeating unit with formula II structure;
Wherein, x is halogen;
Y is 1～16;
The side chain of described functional isotatic polypropylene is at homonymy.
2. functional isotatic polypropylene according to claim 1, is characterized in that, the described repeating unit with formula II structure is greater than zero and be less than or equal to 11.7mol% in the insertion rate of described functional isotatic polypropylene.
3. the preparation method of claim 1 or 2 described functional isotatic polypropylene comprises:
Under the effect of catalyzer and promotor, propylene and the haloolefin with formula III structure are carried out to polymerization in inert solvent, obtain functional isotatic polypropylene; Described catalyzer is the lutidine amine hafnium complexes with formula IV structure, and described promotor is triphen carbon four (pentafluorophenyl group) borate;
Wherein, x is halogen;
Y is 1～16;
R
1, R
2with R
3be selected from independently of one another the different alkyl of hydrogen or C1～C10.
4. preparation method according to claim 3, is characterized in that, described lutidine amine hafnium complexes and the boratory mol ratio of described triphen carbon four (pentafluorophenyl group) are 1:(1～4).
5. preparation method according to claim 3, is characterized in that, the temperature of described polymerization is 0～100 ℃, and the time of described polymerization is 10～60min.
6. preparation method according to claim 3, is characterized in that, described inert solvent is hydro carbons, cyclic hydrocar-bons or aromatic hydrocarbons.
7. preparation method according to claim 3, is characterized in that, described lutidine amine hafnium complexes is 1:(300～1500 with the mol ratio with haloolefin of formula III structure).
8. preparation method according to claim 3, is characterized in that, in the process of described polymerization, also can comprise pickling agent, and described pickling agent is alkylaluminium cpd.
9. preparation method according to claim 8, is characterized in that, the mol ratio of described lutidine amine hafnium complexes and described alkylaluminium cpd is 1:(50～400).
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| CN107098997A (en) * | 2017-03-26 | 2017-08-29 | 天津大学 | A kind of isotactic polypropylene containing ammonium ion is from aggressiveness and preparation method |
| CN112625161A (en) * | 2020-12-03 | 2021-04-09 | 万华化学集团股份有限公司 | Self-crosslinking flame-retardant polypropylene material and preparation method thereof |
| CN112724343A (en) * | 2021-01-19 | 2021-04-30 | 天津大学 | Polyolefin block copolymer and preparation method thereof |
| CN113527352A (en) * | 2020-04-17 | 2021-10-22 | 中国石油天然气股份有限公司 | Pyridine amino hafnium compound and preparation method and application thereof |
| WO2022106688A1 (en) * | 2020-11-23 | 2022-05-27 | Sabic Global Technologies B.V. | Solution process for production of halide- or tertiary amine- functionalized polyolefins |
| CN114874370A (en) * | 2022-06-13 | 2022-08-09 | 中国科学院长春应用化学研究所 | Ultrahigh molecular weight functionalized isotactic polypropylene and preparation method thereof |
| CN115947882A (en) * | 2023-03-14 | 2023-04-11 | 江苏欣诺科催化剂股份有限公司 | Preparation method of pyridine amido hafnium catalyst |
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| CN114874370B (en) * | 2022-06-13 | 2023-05-26 | 中国科学院长春应用化学研究所 | Ultra-high molecular weight functionalized isotactic polypropylene and preparation method thereof |
| CN115947882A (en) * | 2023-03-14 | 2023-04-11 | 江苏欣诺科催化剂股份有限公司 | Preparation method of pyridine amido hafnium catalyst |
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