CN103483482B - 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 a kind of Functional isotactic polypropylene and preparation method thereof.In the process of preparation Functional isotactic polypropylene, polymerization single polymerization monomer propylene is polymerized under the effect of catalyzer with promotor with the 1-alkene of end halo, thus obtain Functional isotactic polypropylene, wherein said catalyzer is lutidine amine hafnium complexes, and promotor is triphen carbon four (pentafluorophenyl group) borate.Because the catalyst system of catalyzer and promotor is high to the solid of polymerization single polymerization monomer, regioselectivity, and to the halo 1-alkene of long-chain, there is fabulous copolymerized ability, the regularity of the Functional isotactic polypropylene therefore prepared is higher, and degree of isotacticity ([mmmm]) is greater than 99%.
Description
Technical field
The present invention relates to polypropylene technology field, particularly relate to a kind of Functional isotactic polypropylene and preparation method thereof.
Background technology
Polypropylene is a kind of thermoplastic resin obtained by propylene polymerization, and by methyl arrangement position, 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 the both sides that methyl is arranged in molecular backbone chain claim Atactic Polypropelene out of orderly; The both sides being 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.Compared with other thermoplastic resins, the features 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 packaging, 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 isotactic polypropylene is more excellent.Such as, by the isotactic directional property copolymerization of propylene and ω-halogen-alpha-olefin obtain containing the Functional isotactic polypropylene hanging halogen group, while retaining excellent physical and mechanical properties, the nonpolar defect of polypropylene can be improved, the wetting ability of effective Reinforced Polypropylene, colourability, static resistance and the performance such as consistency and clinging power with polar macromolecule material, improve its added value.Containing the multipolymer hanging halogen group, there is active reaction site, by the reaction of class click chemistry, halogen group can be converted into other various polarity group easily and efficiently, thus obtain diversified Functional isotactic polypropylene material.
From the sixties in last century so far, numerous research group adopts heterogeneous Ziegler-Natta catalyst or catalyzed by homogeneous metallocene catalyst to carry out the copolymerization of propylene and ω-halogen-alpha-olefin.Such as, Bacskai etc. adopt TiCl
3/ Et
2alCl catalyst system carries out the copolymerization of propylene and multiple ω-halogen-alpha-olefin, and in gained multipolymer, the most high-content of halogen group reaches 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 be difficult to ensure high degree of isotacticity.Recently, Kashiwa research group uses Et (Ind)
2zrCl
2/ MAO system catalysis the copolymerization of propylene and the bromo-1-undecylene of 11-, in gained multipolymer, the content of bromine group is between 1.5 ~ 10.3mol%, and molecular weight is at 11.2 ~ 19.6kgmol
-1between (polymkeric substance circulate a notice of, Polym.Bull.2007,59,177).Although in metallocene catalysis system gained multipolymer, the content of halogen group can reach very high, and the molecular weight of polymkeric substance is less than 20kgmol
-1, and the double bond owing to producing containing the structural unit inserted by different way and β-hydrogen or halogen eliminative reaction, 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 isotactic polypropylene and preparation method thereof.
In view of this, the invention provides a kind of Functional isotactic 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 isotactic polypropylene is at homonymy.
Preferably, the repeating unit described in formula II structure is greater than zero in the insertion rate of described Functional isotactic polypropylene and is less than or equal to 11.7mol%.
Present invention also offers the preparation method of described Functional isotactic polypropylene, comprising:
Under the effect of catalyzer and promotor, propylene is polymerized with the haloolefin with formula III structure in inert solvent, obtains Functional isotactic 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 the different alkyl of hydrogen or C1 ~ C10 independently of one another.
Preferably, described lutidine amine hafnium complexes and described triphen carbon four (pentafluorophenyl group) boratory mol ratio are 1:(1 ~ 4).
Preferably, the temperature of described polymerization is 0 ~ 100 DEG C, 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 of the haloolefin with 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 isotactic polypropylene, in the process of preparation Functional isotactic polypropylene, the present invention adopts catalyzer to be lutidine amine hafnium complexes, promotor is that triphen carbon four (pentafluorophenyl group) boratory catalyst system catalyzing propone is when being polymerized with the haloolefin with formula III structure, solid, regioselectivity are high, and to halo 1-alkene, there is fabulous copolymerized ability, better to the tolerance of some haloolefin, there is not the side reactions such as β-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 high reactivity polypropylene, and has fabulous copolymerized ability to the halo 1-alkene of long-chain.Experimental result shows, have the insertion rate of the repeating unit of formula II structure in the present invention for being greater than zero and being less than or equal to 11.7mol%, the melt temperature of Functional isotactic polypropylene is 82 ~ 155 DEG C, and weight-average molecular weight is 66 ~ 144kgmol
-1.
Accompanying drawing explanation
Fig. 1 is the Functional isotactic polypropylene of the embodiment of the present invention 1 preparation
13c NMR spectrogram;
Fig. 2 is the Functional isotactic polypropylene of the embodiment of the present invention 1 preparation
1h NMR spectrogram;
Fig. 3 is the typical gel permeation chromatography graphic representation of Functional isotactic polypropylene prepared by the present invention;
Fig. 4 is the typical differential thermal analysis curve figure of Functional isotactic polypropylene prepared by the present invention.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses a kind of Functional isotactic 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 isotactic polypropylene is at homonymy.
In described Functional isotactic polypropylene, described x is preferably Cl, Br and I, and described y is the number of the repeating unit methylene with formula II structure, is preferably 8 ~ 16.
According to the present invention, the degree of isotacticity of described Functional isotactic polypropylene is close to 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 DEG C; The described insertion rate of repeating unit in described isotatic polypropylene with formula II structure is greater than zero and is less than or equal to 11.7mol%.
In the present invention, described Functional isotactic polypropylene wherein a part of segment can have formula (V) ~ formula (Ⅺ) structure:
Present invention also offers the preparation method of described Functional isotactic polypropylene, comprising:
Under the effect of catalyzer and promotor, propylene is polymerized with the haloolefin with formula III structure in inert solvent, obtains Functional isotactic 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 the different alkyl of hydrogen or C1 ~ C10 independently of one another.
The present invention is in the process of preparation Functional isotactic polypropylene, adopt catalyzer to be lutidine amine hafnium complexes and promotor be triphen carbon four (pentafluorophenyl group) borate catalyst system catalyzing propone and there is the alkene of formula III structure and the 1-olefinic polymerization of end halo, thus obtained Functional isotactic polypropylene.
In the process of the described Functional isotactic polypropylene of preparation, all compounds to moisture and oxygen sensitivity are all in MBraun glove box or utilize standard Schlenk technique 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 hydrogen, methyl, sec.-propyl or the tertiary butyl independently of one another.Described lutidine amine hafnium complexes and described triphen carbon four (pentafluorophenyl group) boratory mol ratio are preferably 1:(1 ~ 4), be more preferably 1:(2 ~ 3); The mol ratio of the 1-alkene of described catalyzer and described end halo is preferably 1:(300 ~ 1500), be more preferably 1:(700 ~ 1400).
Of the present invention being aggregated in inert solvent is carried out, and namely adopts the method for solution polymerization to be polymerized; Described inert solvent is preferably hydro carbons, cyclic hydrocar-bons or aromatic hydrocarbons, is more preferably toluene.The temperature of described polymerization is preferably 0 ~ 100 DEG C, is more preferably 25 ~ 75 DEG C, and the time of described polymerization is preferably 10 ~ 60min, is more preferably 20 ~ 40min.The present invention in the course of the polymerization process, also add pickling agent, described pickling agent is preferably alkylaluminium cpd, is more preferably triisobutyl aluminium, described alkylaluminium cpd in the course of the polymerization process can impurity in cleaning reaction system, 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), be more preferably 1:(100 ~ 300); Most preferably be 1:(150 ~ 250).
Concrete reaction conditions prepared by described Functional isotactic polypropylene and step as follows:
Under propylene atmosphere, dry toluene is added successively in the polymerization reactor of drying, the 1-alkene of end halo and the toluene solution of triisobutyl aluminium, after stirring 10 ~ 20min at a set temperature, add the mixture initiation reaction (total liquor capacity is 40mL) of catalyzer and promotor, continue to pass into propylene and keep propylene pressure to be 1 normal atmosphere, after reaction 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.Filter dry 24 ~ 36h at putting into vacuum drying oven 60 ~ 80 DEG C after the product that obtains adopts washing with acetone 3 times, namely obtain Functional isotactic polypropylene.
The preparation of Functional isotactic polypropylene described in the present invention can be carried out according to following reaction formula:
The application, in the process detected the Functional isotactic polypropylene of preparation, adopts NMR (Nuclear Magnetic Resonance) spectrum to measure the molecular structure of multipolymer; Differential thermal analysis is adopted 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 at 120 DEG C by Varian Unity-400 type nuclear magnetic resonance spectrometer, and TMS is interior mark, and deuterated orthodichlorobenzene is solvent.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
xthe integral area of representative at xppm peak place, 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) measured by Perkin-ElmerPyris1DSC differential scanning calorimeter, temperature rate is 10 DEG C/min, rescan.Gel permeation chromatography (GPC) refers to that the molecular weight and molecualr weight distribution index of polymkeric substance is measured by PLGPC-220 type gel permeation chromatograph; Adopt RI-Laser detector, three packed columns are the chromatographic column of Plgel10 μm of MIXED-BLS, solvent is 1,2,4-trichlorobenzene (TCB), and add 2 of 0.05wt%, 6-di-tert-butyl-4-methy phenol (BHT) makes oxidation inhibitor, probe temperature is 150 DEG C, and flow velocity is 1.0mL/min, adopts PL EasiCal PS-1 to be standard specimen.
The application, in the process of preparation Functional isotactic polypropylene, selects lutidine amine hafnium complexes to be 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 high reactivity polypropylene, and has fabulous copolymerized ability to the 1-alkene of long-chain.Under the effect of the catalyzer of copolymerized ability excellence, by the 1-olefin-copolymerization of propylene and halo, obtain the clear and definite high molecular high isotactic of structure ([mmmm] >99%) containing the Functional isotactic polypropylene enriching halogen group.The weight-average molecular weight of Functional isotactic polypropylene is 66.0 ~ 144kg/mol, and molecular weight distributing index (PDI) is 1.81 ~ 2.65.The insertion rate of polar monomer can regulate being greater than zero and being less than or equal between 11.7mol%, and the melt temperature of multipolymer can regulate between 82 ~ 155 DEG C.
Compared with the Functional isotactic polypropylene of the Halogen group elements of bibliographical information, Functional isotactic polypropylene prepared by the present invention is while the high polar group content of guarantee, the regularity of molecular weight and molecular chain structure significantly improves, when this is the 1-olefinic polymerization due to selected catalyst system catalyzing propone and end halo, solid, regioselectivity are high, and to the halo 1-alkene of long-chain, there is fabulous copolymerized ability, better to the tolerance of some haloolefin, there is not the side reactions such as β-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 to understand the present invention further, below in conjunction with embodiment, the preparation method to Functional isotactic polypropylene provided by the invention is described in detail, and 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 obtained by MBraun SPS solvent purification treatment system; The method preparation that the pyridine amine hafnium complexes reference literature (macromole, Macromolecules2007,40,3510) adopted describes, other raw materials are commercially available prod.
Embodiment 1
Under propylene atmosphere, in dry polymerization reactor, add 30mL dry toluene successively, 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 DEG C of temperature after, add 5 μm of ol catalyzer lutidine amine hafnium complexes (R
1, R
2with R
3be all sec.-propyl) and 10 μm of ol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) mixture initiation reaction, total liquor capacity is 40mL, continues to pass into propylene and keeps propylene pressure to be 1 normal atmosphere, after reaction 10min, pours reaction solution containing 10%(V/V into) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer; Filter the product that obtains to put into dry 24h at vacuum drying oven 60 DEG C after washing with acetone 3 times, 0.32g polymkeric substance of weighing to obtain, the catalytic activity of polymkeric substance is 3.80 × 10
5g/mol
hfh, relative weight average molecular weight is 134kg/mol, and relative molecular weight distribution index is 1.97, passes through
1the insertion rate that H NMR spectrum elucidation calculates the iodo-1-undecylene of 11-is that 11.7mol%, DSC test shows that the melt temperature of this sample is 82 DEG C.As shown in Figure 1, Fig. 1 is propylene/11-iodo-1-undecylene multipolymer
13c NMR spectrogram; As shown in Figure 2, Fig. 2 is propylene/11-iodo-1-undecylene multipolymer of the embodiment of the present invention 1 preparation
1h NMR spectrogram; As shown in Figure 4, Fig. 4 is the typical DSC graphic representation of Functional isotactic polypropylene prepared by the present invention, and in figure, curve c is the DSC curve of propylene/11-iodo-1-undecylene multipolymer prepared by embodiment 1, and curve a is the DSC curve of isotatic polypropylene.
Embodiment 2
Under propylene atmosphere, in dry polymerization reactor, add 30mL dry toluene successively, the iodo-1-undecylene of 3.7mmol11-and 1.0mL Al (
ibu)
3toluene solution (0.5M), stir 10min at 25 DEG C of temperature after, add 5 μm of ol catalyzer lutidine amine hafnium complexes (R
1, R
2with R
3be all sec.-propyl) and 10 μm of ol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) mixture initiation reaction, total liquor capacity is 40mL, continues to pass into propylene and keeps propylene pressure to be 1 normal atmosphere, after reaction 10min, pours reaction solution containing 10%(V/V into) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer; Filter the product that obtains to put into dry 24h at vacuum drying oven 60 DEG C after washing with acetone 3 times, 0.5g polymkeric substance of weighing to obtain, the catalytic activity of polymkeric substance is 6.00 × 10
5g/mol
hfh, relative weight average molecular weight is 130kg/mol, and relative molecular weight distribution index is 1.81, passes through
1the insertion rate that H NMR spectrum elucidation calculates the iodo-1-undecylene of 11-is that 7.50mol%, DSC test shows that the melt temperature of this sample is 105 DEG C.As described in Figure 3, Fig. 3 is the GPC graphic representation of Functional isotactic polypropylene prepared by the present invention, the GPC graphic representation of propylene/11-iodo-1-undecylene multipolymer that a is prepared for the embodiment of the present invention 2 in figure; Fig. 4 is the typical DSC graphic representation of Functional isotactic polypropylene prepared by the present invention, and in figure, curve b is the DSC curve of propylene/11-iodo-1-undecylene multipolymer prepared by embodiment 2.
Embodiment 3
Under propylene atmosphere, in dry polymerization reactor, add 30mL dry toluene successively, the iodo-1-undecylene of 1.5mmol11-and 1.0mL Al (
ibu)
3toluene solution (0.5M), stir 10min at 25 DEG C of temperature after, add 5 μm of ol catalyzer lutidine amine hafnium complexes (R
1, R
2with R
3be all sec.-propyl) and 10 μm of ol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) mixture initiation reaction, total liquor capacity is 40mL, continues to pass into propylene and keeps propylene pressure to be 1 normal atmosphere, after reaction 10min, pours reaction solution containing 10%(V/V into) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer; Filter and to put into dry 24h at vacuum drying oven 60 DEG C after the product that obtains adopts washing with acetone 3 times, 0.72g polymkeric substance of weighing to obtain, the catalytic activity of polymkeric substance is 8.60 × 10
5g/mol
hfh, relative weight average molecular weight is 144kg/mol, and relative molecular weight distribution index is 2.03, passes through
1the insertion rate that H NMR spectrum elucidation calculates the iodo-1-undecylene of 11-is that 3.00mol%, DSC test shows that the melt temperature of this sample is 127 DEG C.
Embodiment 4
Under propylene atmosphere, in dry polymerization reactor, add 30mL dry toluene successively, the iodo-1-undecylene of 3.7mmol11-and 1.5mL Al (
ibu)
3toluene solution (0.5M), stir after 10 minutes at 25 DEG C of temperature, add 5 μm of ol catalyzer lutidine amine hafnium complexes (R
1, R
2with R
3be all sec.-propyl) and 10 μm of ol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) mixture initiation reaction, total liquor capacity is 40mL, continues to pass into propylene and keeps propylene pressure to be 1 normal atmosphere, after reaction 10min, pours reaction solution containing 10%(V/V into) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer.Filter the product that obtains to put into dry 24h at vacuum drying oven 60 DEG C after washing with acetone 3 times, 0.54g polymkeric substance of weighing to obtain, catalytic activity is 6.50 × 10
5g/mol
hfh, relative weight average molecular weight is 101kg/mol, and relative molecular weight distribution index is 2.45, passes through
1the insertion rate that H NMR spectrum elucidation calculates the iodo-1-undecylene of 11-is that 7.00mol%, DSC test shows that the melt temperature of this sample is 108 DEG C.As described in Figure 3, Fig. 3 is the typical GPC graphic representation of Functional isotactic polypropylene prepared by the present invention, and in figure, b is the GPC graphic representation of propylene/11-iodo-1-undecylene multipolymer prepared by the embodiment of the present invention 4.
Embodiment 5
Under propylene atmosphere, in the polymerization reactor of drying, add 30mL dry toluene successively, the iodo-1-undecylene of 3.7mmol11-and 2.0mL Al (
ibu)
3toluene solution (0.5M), stir 10min at 25 DEG C of temperature after, add 5 μm of ol catalyzer lutidine amine hafnium complexes (R
1, R
2with R
3be all sec.-propyl) and 10 μm of ol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) mixture initiation reaction, total liquor capacity is 40mL, continues to pass into propylene and keeps propylene pressure to be 1 normal atmosphere, after reaction 10min, pours reaction solution containing 10%(V/V into) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer; Filter the product that obtains to put into dry 24h at vacuum drying oven 60 DEG C after washing with acetone 3 times, 0.35g polymkeric substance of weighing to obtain, the catalytic activity of polymkeric substance is 4.20 × 10
5g/mol
hfh, relative weight average molecular weight is 66kg/mol, and relative molecular weight distribution index is 2.65, passes through
1the insertion rate that H NMR spectrum elucidation calculates the iodo-1-undecylene of 11-is that 7.20mol%, DSC test shows that the melt temperature of this sample is 101 DEG C.As described in Figure 3, Fig. 3 is the typical GPC graphic representation of Functional isotactic polypropylene prepared by the present invention, and in figure, c is the GPC graphic representation of propylene/11-iodo-1-undecylene multipolymer prepared by the embodiment of the present invention 5.
Embodiment 6
Under propylene atmosphere, in the polymerization reactor of drying, add 30mL dry toluene successively, the iodo-1-butylene of 3.7mmol4-and 1.0mL Al (
ibu)
3toluene solution (0.5M), stir 10min at 25 DEG C of temperature after, add 5 μm of ol catalyzer lutidine amine hafnium complexes (R
1, R
2for sec.-propyl, R
3for hydrogen) and 10 μm of ol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) mixture initiation reaction, total liquor capacity is 40mL, continues to pass into propylene and keeps propylene pressure to be 1 normal atmosphere, after reaction 10min, pours reaction solution containing 10%(V/V into) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer; Filter the product that obtains to put into dry 24h at vacuum drying oven 60 DEG C after washing with acetone 3 times, 0.10g polymkeric substance of weighing to obtain, the catalytic activity of polymkeric substance is 1.20 × 10
5g/mol
hfh, relative weight average molecular weight is 80.0kg/mol, and relative molecular weight distribution index is 2.32, passes through
1the insertion rate that H NMR spectrum elucidation calculates the iodo-1-butylene of 4-is that 1.80mol%, DSC test shows that the melt temperature of this sample is 135 DEG C.
Embodiment 7
Under propylene atmosphere, in the polymerization reactor of drying, add 30mL dry toluene successively, the bromo-1-undecylene of 3.7mmol11-and 1.0mL Al (
ibu)
3toluene solution (0.5M), stir 10min at 25 DEG C of temperature after, add 5 μm of ol catalyzer lutidine amine hafnium complexes (R
1, R
2for sec.-propyl, R
3for hydrogen) and 10 μm of ol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) mixture initiation reaction, total liquor capacity is 40mL, continues to pass into propylene and keeps propylene pressure to be 1 normal atmosphere, after reaction 10min, pours reaction solution containing 10%(V/V into) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer; Filter the product that obtains to put into dry 24h at vacuum drying oven 60 DEG C after washing with acetone 3 times, 0.09g polymkeric substance of weighing to obtain, the catalytic activity of polymkeric substance is 1.10 × 10
5g/mol
hfh, relative weight average molecular weight is 121kg/mol, and relative molecular weight distribution index is 2.10, passes through
1the insertion rate that H NMR spectrum elucidation calculates the bromo-1-undecylene of 11-is that 3.40mol%, DSC test shows that the melt temperature of this sample is 119 DEG C.
Embodiment 8
Under propylene atmosphere, in the polymerization reactor of drying, add 30mL dry toluene successively, the chloro-1-undecylene of 3.7mmol11-and 1.0mL Al (
ibu)
3toluene solution (0.5M), stir 10min at 25 DEG C of temperature after, add 5 μm of ol catalyzer lutidine amine hafnium complexes (R
1, R
2for sec.-propyl, R
3for hydrogen) and 10 μm of ol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) mixture initiation reaction, total liquor capacity is 40mL, continues to pass into propylene and keeps propylene pressure to be 1 normal atmosphere, after reaction 10min, pours reaction solution containing 10%(V/V into) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer; Filter the product that obtains to put into dry 24h at vacuum drying oven 60 DEG C after washing with acetone 3 times, 0.04g polymkeric substance of weighing to obtain, the catalytic activity of polymkeric substance is 0.50 × 10
5g/mol
hfh, relative weight average molecular weight is 108kg/mol, and relative molecular weight distribution index is 2.97, passes through
1the insertion rate that H NMR spectrum elucidation calculates the chloro-1-undecylene of 11-is that 3.00mol%, DSC test shows that the melt temperature of this sample is 119 DEG C.
Embodiment 9
Under propylene atmosphere, in the polymerization reactor of drying, add 30mL dry toluene successively, 3.7mmol19-iodo-1-19 carbene and 1.0mL Al (
ibu)
3toluene solution (0.5M), stir 10min at 25 DEG C of temperature after, add 5 μm of ol catalyzer lutidine amine hafnium complexes (R
1, R
2for the tertiary butyl, R
3for hydrogen) and 10 μm of ol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) mixture initiation reaction, total liquor capacity is 40mL, continues to pass into propylene and keeps propylene pressure to be 1 normal atmosphere, after reaction 10min, pours reaction solution containing 10%(V/V into) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer; Filter the product that obtains to put into dry 24h at vacuum drying oven 60 DEG C after washing with acetone 3 times, 0.6g polymkeric substance of weighing to obtain, the catalytic activity of polymkeric substance is 7.20 × 10
5g/mol
hfh, relative weight average molecular weight is 145kg/mol, and relative molecular weight distribution index is 2.07, passes through
1the insertion rate that H NMR spectrum elucidation calculates 19-iodo-1-19 carbene is that 8.50mol%, DSC test shows that the melt temperature of this sample is 102 DEG C.
Embodiment 10
Under propylene atmosphere, in the polymerization reactor of drying, add 30mL dry toluene successively, 3.7mmol19-bromo-1-19 carbene and 1.0mL Al (
ibu)
3toluene solution (0.5M), stir 10min at 25 DEG C of temperature after, add 5 μm of ol catalyzer lutidine amine hafnium complexes (R
1, R
2for the tertiary butyl, R
3for hydrogen) and 10 μm of ol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) mixture initiation reaction, total liquor capacity is 40mL, continues to pass into propylene and keeps propylene pressure to be 1 normal atmosphere, after reaction 10min, pours reaction solution containing 10%(V/V into) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer.Filter the product that obtains to put into dry 24h at vacuum drying oven 60 DEG C after washing with acetone 3 times, 0.3g polymkeric substance of weighing to obtain, the catalytic activity of polymkeric substance is 3.60 × 10
5g/mol
hfh, relative weight average molecular weight is 105kg/mol, and relative molecular weight distribution index is 1.96, passes through
1the insertion rate that H NMR spectrum elucidation calculates 19-bromo-1-19 carbene is that 5.40mol%, DSC test shows that the melt temperature of this sample is 112 DEG C.
Embodiment 11
Under propylene atmosphere, in the polymerization reactor of drying, add 30mL dry toluene successively, 3.7mmol19-chloro-1-19 carbene and 1.0mL Al (
ibu)
3toluene solution (0.5M), stir after 10 minutes at 25 DEG C of temperature, add 5 μm of ol catalyzer lutidine amine hafnium complexes (R
1, R
2for the tertiary butyl, R
3for hydrogen) and 10 μm of ol promotor triphen carbon four (pentafluorophenyl group) borate ([Ph
3c] [B (C
6f
5)
4]) mixture initiation reaction, total liquor capacity is 40mL, continues to pass into propylene and keeps propylene pressure to be 1 normal atmosphere, reacting after 10 minutes, pour reaction solution containing 10%(V/V into) in the ethanolic soln of hydrochloric acid, separate out a large amount of white polymer; Filter the product that obtains to put into after washing with acetone 3 times at vacuum drying oven 60 DEG C dry 24 hours, 0.2g polymkeric substance of weighing to obtain, the catalytic activity of polymkeric substance is 2.40 × 10
5g/mol
hfh, relative weight average molecular weight is 102kg/mol, and relative molecular weight distribution index is 1.97, passes through
1the insertion rate that HNMR spectrum elucidation calculates 19-chloro-1-19 carbene is that 4.90mol%, DSC test shows that the melt temperature of this sample is 114 DEG C.
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.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (9)
1. a Functional isotactic polypropylene, comprises 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 isotactic polypropylene is at homonymy.
2. Functional isotactic polypropylene according to claim 1, is characterized in that, described in there is formula II structure repeating unit be greater than zero in the insertion rate of described Functional isotactic polypropylene and be less than or equal to 11.7mol%.
3. the preparation method of the Functional isotactic polypropylene described in claim 1 or 2, comprising:
Under the effect of catalyzer and promotor, propylene is polymerized with the haloolefin with formula III structure in inert solvent, obtains Functional isotactic 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 the different alkyl of hydrogen or C1 ~ C10 independently of one another.
4. preparation method according to claim 3, is characterized in that, described lutidine amine hafnium complexes and described triphen carbon four (pentafluorophenyl group) boratory mol ratio are 1:(1 ~ 4).
5. preparation method according to claim 3, is characterized in that, the temperature of described polymerization is 0 ~ 100 DEG C, and the time of described polymerization is 10 ~ 60min.
6. preparation method according to claim 3, is characterized in that, described inert solvent is 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 of the haloolefin with formula III structure).
8. preparation method according to claim 3, is characterized in that, also can comprise pickling agent in the process of described polymerization, 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 |
| 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 |
| CN116438211A (en) * | 2020-11-23 | 2023-07-14 | Sabic环球技术有限责任公司 | Solution process for producing halo-or tertiary amine-functionalized polyolefins |
| CN112625161B (en) * | 2020-12-03 | 2022-07-12 | 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 |
| 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 |
| CN115947882B (en) * | 2023-03-14 | 2023-05-23 | 江苏欣诺科催化剂股份有限公司 | Preparation method of pyridine amino hafnium catalyst |
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| CN102245650A (en) * | 2008-12-12 | 2011-11-16 | 道达尔石油化学产品研究弗吕公司 | Preparation of long-chain branched isotactic polypropylene |
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| CN101379100A (en) * | 2005-08-25 | 2009-03-04 | 康奈尔大学 | Production of isotactic and regiorandom polypropylene based polymer and block copolmyers |
| EP2046842A2 (en) * | 2006-07-31 | 2009-04-15 | Fina Technology, Inc. | Isotactic-atactic polypropylene and methods of making same |
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