CN109456445A - A kind of pectination propylene based polyolefm process for preparation of thermoplastic elastomer - Google Patents
A kind of pectination propylene based polyolefm process for preparation of thermoplastic elastomer Download PDFInfo
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- CN109456445A CN109456445A CN201811148679.3A CN201811148679A CN109456445A CN 109456445 A CN109456445 A CN 109456445A CN 201811148679 A CN201811148679 A CN 201811148679A CN 109456445 A CN109456445 A CN 109456445A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Abstract
The invention discloses a kind of pectination propylene based polyolefm thermoplastic elastomer (TPE)s and preparation method thereof, the pectination polyolefin thermoplastic elastomer is side chain, unformed ethylene/propene copolymer soft segment for main chain using the polypropylene hard section crystallized, pass through tandem catalyst system, pass through the polypropylene polymeric monomer of first reactor synthetic crystallization first in high temperature and pressure solution polymerisation system, synthesized polymeric monomer, which enters in second reactor, carries out ternary polymerization with ethylene, propylene, synthesizes the pectination propylene based polyolefm thermoplastic elastomer (TPE).Pectination ethylene based polyolefin thermoplastic elastomer (TPE) prepared by the present invention can be used for substituting the application field of conventional polyolefins thermoplastic elastomer (TPE), have a high industrial value.
Description
Technical field
The invention belongs to the preparation technical fields of thermoplastic elastomer (TPE), are related to a kind of pectination propylene based polyolefm thermoplastic elastomehc
The preparation method of property body.
Background technique
Relatively good mechanical property is needed by vulcanization crosslinking traditional rubber in order to obtain, and this chemical crosslinking is so that rubber
It is difficult recycling and reusing, causes very serious environmental pollution.The forties in last century starts thermoplastic elastomer (TPE) occurred
(TPE), the difference of it and vulcanized rubber is to be physical crosslinking.TPE has the elasticity of rubber at normal temperature, at high temperature again can be with
Thermoplastic shaping, it has also become " third generation rubber " after natural rubber and synthetic rubber.Wherein account for TPE total output 30% or so
Polyolefin-type thermoplastic elastomer (TPE), because having good chemical resistance, good weatherability, light-weight and can continuous production etc.
Advantage is widely used in the fields such as automobile, electronics, electrical and daily necessities.
The ethylene/alpha-olefin copolymer of high co-monomer insertion --- polyolefin elastomer (POE) is a kind of with high attached
Value added industrialization product.It, which is (Dow) company, Dow company first, uses constrained geometry by INSITE technique
(EP 0416815) is made in metallocene catalyst (CGC), trade name ENGAGETM, product is with narrow molecular weight distribution, copolymerization list
The advantages that body is evenly distributed, processing performance is excellent.Subsequent Exxon Mobil (ExxonMobil) uses bridging dicyclopentadiene metal catalytic
Agent also stand-alone development Ethylene/1-butene, ethylene/1- hexene, ethylene/1- octene copolymer elastomer POE, trade name
ExactTM.In addition, Mitsui chemical industry (Mitusui), South Korea LG chemistry and SK, the Basel Li Ande, Holland
(Lyondellbasell) also all it is proposed POE product.In addition, " chain shuttle " was invented in 2005 by DOW company polymerize skill again
Art, and a kind of completely new polyolefin thermoplastic elastomer-olefin block copolymers (OBC) of the technology successful commercialization are utilized,
Product brand is InfuseTM(Science 2006,312,714-719).There is the product hard section and soft segment to replace on main chain
More block structures, be not only able to maintain the fusing point similar with LLDPE, but also have the elasticity of POE, and can keep at relatively high temperatures compared with
Good elasticity, heat resistance are much larger than POE elastomer.2013, DOW had developed the block copolymerization of acrylic on this basis
Object, trade name INTUNETM.The commodity can be used as compatilizer excellent between polyethylene and polypropylene, be applied to polyethylene
With the recycling of polypropylene material.Polypropylene is more complicated with respect to polyethylene structure, can be given birth to using the metallocene catalyst of different structure
It produces and obtains the polypropylene of isotactic, rule and random three kinds of different structures, and the product property that these three polypropylene show
Differ widely, such as isotactic polypropylene fusing point can achieve 165 DEG C, and the fusing point higher than HDPE, this makes isotactic polypropylene
It can be applied at higher temperatures, widen the use scope of material；Random polypropylene then shows completely unformed
Structure.A certain amount of ethylene segment is inserted into isotactic polypropylene, polymer can turn from thermoplastic to thermoplastic elastomer (TPE)
Become.When the mass fraction of ethylene insertion is in 10-15wt%, material shows the performance of excellent elastomer.(Journal of
Applied Polymer Science, 2007,104,489-499) for this purpose, it is contemplated that can be tied by copolymer chain topology
The design of structure, using crystallizable polypropylene hard section concentrate on the side chain of copolymer, ethylene/propene random copolymer soft segment as
The main chain of copolymer, the hard section of side chain can form the plastics phase of crystallization, main chain forms rubber phase, separate material generation mutually,
Finally synthesize a kind of propylene based polyolefm thermoplastic elastomer (TPE) with pectinate texture.
The production method of industrial ethylene/alpha-olefin copolymer has solwution method, vapor phase method and three kinds of slurry process at present
(Prog.Polym.Sci.2001,26,1287-1336.).But in the POE of high alpha-olefin content production, each major company is adopted
Use high-temperature solution method.POE properties of product obtained by solwution method will be substantially better than the product of vapor phase method including toughness and elasticity.Though
So there is the patent report (US5770664) using slurry process production POE, but since the fusing point of POE is low, it is easily molten in a solvent
Swollen, the easy fused junction group of product there is no the industrial example of slurry process production POE at present.In addition, can polymerize using polymerisation in solution
Preferably regulate and control chain structure in the process, the production of different performance can be synthesized in conjunction with the design of chain structure and the adjusting of polymerization technique
Product.
Summary of the invention
It is an object of the invention to the deficiencies for existing production product and technology, provide a kind of pectination propylene based polyolefm
Process for preparation of thermoplastic elastomer.
The purpose of the present invention is achieved through the following technical solutions: a kind of pectination propylene based polyolefm thermoplastic elastic
The preparation method of body, comprising the following steps:
(1) under the conditions of anhydrous and oxygen-free, into first reactor be added propylene, propylene homo catalyst, co-catalyst and
Organic solvent, polymerization reaction obtain polypropylene polymeric monomer；Polymerization temperature is 60-300 DEG C, polymerization pressure 0.1-10Mpa；With anti-
The stereometer of organic solvent in kettle is answered, the propylene homo catalyst concn is 0.1~100 μm of ol/L, the co-catalysis
The molar ratio of agent and propylene homo catalyst is 50~10000:1, and the input concentration of propylene is 0.1~20mol/L；All materials
Residence time in the first reactor controls in 2~240min, and the weight average molecular weight of obtained polypropylene polymeric monomer is
1000~50000g/mol, molecular weight distributing index are 1.0~5.0, and the control of terminal double bond ratio is polyacrylic 50% or more
Isotacticity [mmmm] or normality [rrrr] control are 50% or more；
(2) polymer solution that polymerization reaction obtains in first reactor enters in second reactor, in anhydrous and oxygen-free item
Under part, addition propylene, ethylene, catalyst for copolymerization, co-catalyst and organic solvent into second reactor, progress ethylene/propene/
The ternary polymerization of polypropylene polymeric monomer, polymerization temperature is 60-300 DEG C, polymerization pressure 0.1-10MPa, with organic in reaction kettle
The concentration of the stereometer of solvent, the catalyst for copolymerization is 0.1~100 μm of ol/L, and the catalyst for copolymerization and propylene are equal
The molar ratio of poly- catalyst is 20:1~1:10, and the molar ratio of the co-catalyst and catalyst for copolymerization is 50~10000:1,
The ethylene feed concentrations are 0.1~20mol/L, and the raw materials components mole ratio of the propylene and ethylene is 0.1~25:1, are owned
The residence time of material in the second reactor controls in 2~240min；Obtained copolymer weight average molecular weight 20000~
500000g/mol, molecular weight distributing index 1.0~10.0, mole content 10~95% in main chain.
Further, the propylene homo catalyst is the metallocene catalyst or rear metallocene catalysis of single active center
Agent, selected from the double tetrahydroindenyl zirconium dichloride of the Asia rac- ethylene abutment, rac- dimethyl-silicon bridging-two (2- methylindenyl) zirconium dichloride,
Rac- dimethyl-silicon bridging-two (2- methyl 4-phenyl-indenyl) zirconium dichloride ,-two indenyl dimethyl of rac- dimethyl-silicon bridging
Hafnium, meso- diphenyl methyl bridging-cyclopentadienyl-fluorenyl-zirconium dichloride, bis- (dimethyl-silicon abutment)-(3,5- diisopropyls
Cyclopentadienyl group)-(4- isopropylcyclopentadienyl) zirconium dichloride, dimethyl-silicon abutment-fluorenyl-tert-butylamino-diformazan
Base titanium, bis- (3- trimethyl silicon substrate salicyl -3,5- difluorophenyl) titanium chloride.
Further, the catalyst for copolymerization is the metallocene catalyst or post-metallocene catalyst of single active center,
Selected from bicyclic pentadiene dimethyl hafnium, double indenyl zirconium dimethyls, sub- ethylene abutment double tetrahydroindenyl zirconium dichlorides, dimethyl silicon bridge
The bis- indenyls of base-, diphenyl carbon abutment-cyclopentadienyl group-tablet held before the breast by officials base zirconium dichloride, dimethyl-silicon abutment-tetramethyl-ring pentadienyl-
It is tert-butylamino-dimethyl titanium, double tetrahydroindenyl zirconium dichlorides, bis- [2- (3', 5'- di-tert-butyl-phenyl)-indenyl] zirconium dichlorides, double
The double indenyl dichloros of (2- methyl -4,5- pheny-indenylzirconium) zirconium dichloride, the bis- phenoxy group zirconiums of bicyclic pentadiene -, dimethyl-silicon abutment
Change zirconium, diphenyl carbon abutment-cyclopentadienyl group-tablet held before the breast by officials base zirconium dichloride, diphenyl carbon abutment-cyclopentadienyl group-(2- dimethylamine
Base-tablet held before the breast by officials base) zirconium dichloride, dimethyl-silicon abutment-tetramethyl-ring pentadienyl-tert-butylamino-dimethyl titanium, dimethyl silicon bridge
Base -3- pyrrole radicals indenyl-tert-butylamino-dimethyl titanium, pentamethylcyclopentadiene base-(2- phenylphenoxy)-titanium chloride,
Pentamethylcyclopentadiene base-(2,6- diisopropyl phenoxy group)-titanium chloride, bis- (3- methyl salicylidenes-phenyl-pentafluoride imines
Base) titanium chloride, bis- (salicylidene-phenyl imido) titanium chloride, dimethyl-silicon abutment -3- pyrrole radicals indenyl-tert-butyl ammonia
Base-dimethyl titanium, [N- (3,5- di-tert-butyl Salicylidene) -2- diphenylphosphoryl group benzene imines] titanium trichloride, (2,3,4- tri-
Hydrogen -8- diphenylphosphoryl group-quinolyl) tribenzyl zirconium.
Further, the co-catalyst is selected from methylaluminoxane, modified methylaluminoxane, three (pentafluorophenyl group) boronations
Close object, triisobutyl aluminium, triethyl aluminum, trimethyl aluminium.
Further, the organic solvent is linear paraffin, isoparaffin, cycloalkane with 4~10 carbon atoms
Or aralkyl hydrocarbon.
Further, the preferred pentane of the organic solvent, isopentane, n-hexane, hexamethylene, normal heptane, isoheptane,
Normal octane, isooctane, n-decane, isomeric alkane hydrocarbon ils, toluene, dimethylbenzene.
Further, polypropylene polymeric monomer terminal double bond ratio preferably 80% or more obtained by step 1.It is polyacrylic etc.
Normality or normality preferably 80% or more.
Further, polymer fracture elongation made from step 2 is greater than 100%, and breaking strength is greater than 1Mpa.
The beneficial effects of the present invention are: the tandem metallocene catalysis system based on high activity, highly selective, high copolymerized ability
High temperature and pressure tandem continuous solution polymerization technology, prepare crystallization polypropylene hard section be side chain, unformed ethylene/propene without
The new type polyolefin thermoplastic elastomer (TPE) that copolymer is main chain is advised, can be used for substituting answering for conventional polyolefins thermoplastic elastomer (TPE)
With field, have a high industrial value.
Specific embodiment
The present invention is illustrated with following specific embodiments, but the scope of the present invention is not limited to following embodiment.
The charging molar concentration used is referred in the present invention, in terms of organic solvent volume, propylene monomer enters reaction
Initial concentration when kettle, raw materials components mole ratio refers to when propylene enters reaction kettle and the initial molar concentration ratio of vinyl monomer.
Embodiment 1~15 is that the double kettles of high temperature and pressure are connected continuous solution polymerizations, in the polymerization reaction kettle of two 300ml into
Row.
Embodiment 1
Major catalyst homopolymerization catalyst uses rac- dimethyl-silicon bridging-two (2- methyl 4-phenyl-indenyl) in this experiment
Zirconium dichloride, catalyst for copolymerization select dimethyl-silicon abutment-tetramethyl-ring pentadienyl-tert-butylamino-dimethyl titanium, help and urge
Agent uses methylaluminoxane, and solvent is Isopar E, and monomer is ethylene and propylene, and polymerization experiment is in double kettles series connection high temperature and pressure
It is carried out in successive soln system.Reaction kettle and pipeline triisobutyl aluminium and Isopar E wiring solution-forming are cleaned before experiment,
To remove water oxygen.Quantitative homopolymerization catalyst, catalyst for copolymerization, co-catalyst are weighed up, is shifted under nitrogen atmosphere protection, respectively
It is stored in respective storage tank with Isopar E wiring solution-forming, solvent Isopar E also is stored in solvent storage tank.
Experimental procedure are as follows: open reaction kettle and pipeline oil bath, 1 temperature of kettle is increased to 120 DEG C, 2 temperature of kettle is increased to 140
DEG C, mixing speed is all set as 1000rpm；It opens the inlet valve and outlet valve of two kettles, opens 1~No. 5 high pressure chemistry metering pump, five
Platform metering pump continuously inputs in reaction kettle according to the flow velocity of setting, wherein propylene, propylene homo catalyst, co-catalyst, molten
Agent continuously enters kettle 1, and 1 discharging of kettle, catalyst for copolymerization, co-catalyst, ethylene, solvent continuously enter kettle 2, and 2 pressure release of kettle discharges
To final product.Reacting kettle inner pressure passes through proportional valve control, stablizes when 1 pressure of kettle and stablizes in 22bar, 2 pressure of kettle
After 20bar, propylene intake valve is opened, propylene controls constant speed by flowmeter and enters two reaction kettles；Open ethylene intake valve, ethylene
Constant speed, which is controlled, by flowmeter enters reaction kettle 2.After system reaches stable, 1 homopolymerization catalyst concentration of kettle is 4 μm of ol/L, helps and urges
Agent concentration is 10mmol/L, and the molar ratio of co-catalyst and major catalyst is 5000, propene feed concentration 0.92mol/
L, temperature in the kettle control pressure in 120 DEG C, kettle control the residence time in 22bar, material in kettle as 8min；Kettle 2 is copolymerized
Catalyst concn is 20 μm of ol/L, cocatalyst concentration 20mmol/L, and the molar ratio of co-catalyst and major catalyst is
The raw materials components mole ratio example of 1000, ethylene feed concentrations 0.39mol/L, propene feed concentration 0.80mol/L, propylene and ethylene
It is 2.05, in 20bar or so, residence time of the material in reaction kettle be for pressure control in 140 DEG C, kettle for temperature in the kettle control
6min.The material flowed continually out after a large amount of acidic ethanols wash for several times, drain, and is dried in vacuo 8 hours at 60 DEG C by filtering
More than.
The molecular weight (Mw and Mn) and its profile exponent (PDI) of polymer measure (PL- using high-temperature gel permeation chromatography
GPC220).With 1,2,4- trichloro-benzenes for solvent, it is made into the polymer solution of 0.1~0.3wt%, at 150 DEG C with narrow molecular-weight
The polystyrene of distribution is that standard specimen measures at 150 DEG C, solvent flow rate 1.0ml/min.Parameter k=is used to all PS standard specimens
5.91 × 10-4, α=0.69, PP parameter k=15.6 × 10-4, α=0.76.
The fusing point (Tm) of copolymer is measured by TA Instruments Q200.Take 5.0~7.0mg polymer samples with 30
DEG C/min is warming up to 190 DEG C, constant temperature 5min is to eliminate thermal history, after then cooling to -90 DEG C, then constant temperature 3min with 10 DEG C/min
190 DEG C are warming up to 10 DEG C/min speed, the fusing point of polymer is obtained from second of heating curve.
In copolymer the average composition of co-monomer using carbon spectrum nuclear-magnetism (13C NMR) it is measured at 125 DEG C, instrument model is
Bruker AC 400.Polymer be made at 150 DEG C mass fraction be 10% deuterated o-dichlorobenzene solution, in advance dissolution 3 to
4 hours, keep sample solution uniform.Instrument parameter is optimized for 90 ° of pulse angle, the decoupling of reversed proton, pulse delay time 8s, receives
Collect time 1.3s and spectrum width 8000Hz, mean scan number is no less than 5000 times.
The uniaxial tensile test of polymer carries out on universal testing machine (German INSTRON 2710-100), test
Temperature is room temperature, rate of extension 50mm/min, 5 groups of retests of each sample progress.Polymer sample rods pass through mould at 170 DEG C
It is molded, it quenches at room temperature, shape and size are cut by cut-off knife and prepared referring to (GBT 1040.3-2006) 5 pattern item, thick
Degree is about 0.3mm.
Embodiment 2
Experiment condition are as follows: after system reaches stable state, the concentration of homopolymerization catalyst is 2 μm of ol/L, cocatalyst concentration in kettle 1
For 10mmol/L, the molar ratio of co-catalyst and homopolymerization catalyst is 10000, and other experiment conditions are the same as embodiment 1.
Embodiment 3
Experiment condition are as follows: after system reaches stable state, the concentration of homopolymerization catalyst is 6 μm of ol/L, cocatalyst concentration in kettle 1
For 10mmol/L, the molar ratio of co-catalyst and homopolymerization catalyst is 2500, and other experiment conditions are the same as embodiment 1.
Embodiment 4
Experiment condition are as follows: after system reaches stable state, the concentration of homopolymerization catalyst is 8 μm of ol/L, cocatalyst concentration in kettle 1
For 10mmol/L, the molar ratio of co-catalyst and homopolymerization catalyst is 1250, and other experiment conditions are the same as embodiment 1.
Embodiment 5
Experiment condition are as follows: after system reaches stable state, the concentration of catalyst for copolymerization is 40 μm of ol/L in kettle 2, and co-catalyst is dense
Spending is 20mmol/L, and the molar ratio of co-catalyst and major catalyst is 500, and other experiment conditions are the same as embodiment 1.
Embodiment 6
Experiment condition are as follows: after system reaches stable state, the concentration of catalyst for copolymerization is 10 μm of ol/L in kettle 2, and co-catalyst is dense
Spending is 20mmol/L, and the molar ratio of co-catalyst and major catalyst is 2000, and other experiment conditions are the same as embodiment 1.
Embodiment 7
Experiment condition are as follows: after system reaches stable state, the pressure of kettle 1 is stablized in 12bar, and the pressure of kettle 2 is stablized in 10bar,
The propene feed concentration of kettle 1 is 0.46mol/L, and the propene feed concentration of kettle 2 is 0.40mol/L, and the input concentration of ethylene is
0.195mol/L, propylene feed and ethylene feed molar ratio are 2.05, and other experiment conditions are the same as embodiment 1.
Embodiment 8
Experiment condition are as follows: after system reaches stable state, the pressure of kettle 1 is stablized in 6bar, and the pressure of kettle 2 is stablized in 5bar, kettle 1
Propene feed concentration be 0.23mol/L, the propene feed concentration of kettle 2 is 0.20mol/L, and the input concentration of ethylene is
0.096mol/L, propylene feed and ethylene feed molar ratio are 2.08, and other experiment conditions are the same as embodiment 1.
Embodiment 9
Experiment condition are as follows: after system reaches stable state, the propene feed concentration of kettle 1 is 0.92mol/L, the propylene feed of kettle 2
Concentration is 0.80mol/L, and the input concentration of ethylene is 0.53mol/L, and propylene feed and ethylene feed molar ratio are 1.50, other
Experiment condition is the same as embodiment 1.
Embodiment 10
Experiment condition are as follows: after system reaches stable state, the propene feed concentration of kettle 1 is 0.92mol/L, the propylene feed of kettle 2
Concentration is 0.80mol/L, and the input concentration of ethylene is 0.64mol/L, and propylene feed and ethylene feed molar ratio are 1.25, other
Experiment condition is the same as embodiment 1.
Embodiment 11
Experiment condition are as follows: after system reaches stable state, the propene feed concentration of propene feed concentration 0.92mol/L, kettle 2 are
0.80mol/L, the input concentration of ethylene are 0.08mol/L, and propylene feed and ethylene feed molar ratio are 10.0, other experiment items
Part is the same as embodiment 1.
Embodiment 12
Experiment condition are as follows: after system reaches stable state, the residence time of kettle 1 is 6min, and the residence time of kettle 2 is 5min,
Its experiment condition is the same as embodiment 1.
Embodiment 13
Experiment condition are as follows: after system reaches stable state, the residence time of kettle 1 is 10min, and the residence time of kettle 2 is 8min,
Its experiment condition is the same as embodiment 1.
Embodiment 14
Experiment condition are as follows: after system reaches stable state, the polymerization temperature of kettle 2 maintains 160 DEG C, the propene feed concentration of kettle 1
For 0.92mol/L, the propene feed concentration of kettle 2 is 0.80mol/L, and the input concentration of ethylene is 0.39mol/L, propylene feed with
Ethylene feed molar ratio is 2.05, and other experiment conditions are the same as embodiment 1.
Embodiment 15
Experiment condition are as follows: change catalyst for copolymerization is diphenyl carbon abutment-cyclopentadienyl group-tablet held before the breast by officials base zirconium dichloride, other
Experiment condition is the same as embodiment 1.
Embodiment 16 is high temperature and pressure batch copolymerisation, is carried out in the alkene batch polymerization reactor of 500ml.
Embodiment 16
Major catalyst homopolymerization catalyst uses rac- dimethyl-silicon bridging-two (2- methyl 4-phenyl-indenyl) in this experiment
Zirconium dichloride, catalyst for copolymerization select dimethyl-silicon abutment-tetramethyl-ring pentadienyl-tert-butylamino-dimethyl titanium, help and urge
Agent uses methylaluminoxane, and solvent is Isopar E, and monomer is ethylene and propylene, and polymerization experiment is in high temperature and pressure batch solution
It is carried out in system.After first reaction kettle being vacuumized repeatedly-being led to nitrogen displacement before experiment at 100 DEG C 6 hours, then vacuumize logical third
Alkene is replaced three times, is made entire pipeline, is reached sealing, anhydrous and oxygen-free requirement in reaction kettle.
Experimental procedure are as follows: reaction kettle is first warming up to 120 DEG C and then turns on liquid feedstock valve, is added into reaction kettle
220ml solvent Isopar E, co-catalyst 10mmol, immediately closing liquid inlet valve, opens stirring to 1000 revs/min
Clock homopolymerization catalyst is added in reaction kettle by pressure difference, pressure increases to rapidly in kettle after temperature in the kettle rises to reaction temperature
1.0MPa, the amount that hereafter kettle inner propene consumes in reaction process guarantee that pressure is constant in kettle by flow controller sustaining supply.
Constant temperature and pressure reacts 10min, then catalyst for copolymerization is added in reaction kettle by pressure difference, opens ethylene intake valve, the reaction was continued
Gas feed valve is closed after 30min and opens gas blow valve pressure release, then opens liquid outlet valve, material is poured into equipped with big
In the beaker for measuring acidic ethanol.Polymer through filtering, and with ethanol washing for several times after, be dried in vacuo 8 hours or more at 60 DEG C.
In this experiment in kettle homopolymerization catalyst concentration be 2 μm of ol/L, the concentration that catalyst for copolymerization helps be 10 μm of ol/L, third
The raw materials components mole ratio of alkene and ethylene is 2.05.All materials used in experiment are through water removal deoxygenation processing.
Embodiment 17 is the high temperature and pressure series connection continuous solution polymerization of two reactors, and two reaction units are respectively
The annular-pipe reactor of 300ml and the polymerization reaction kettle of 300ml.
Embodiment 17
Major catalyst homopolymerization catalyst uses rac- dimethyl-silicon bridging-two (2- methyl 4-phenyl-indenyl) in this experiment
Zirconium dichloride, catalyst for copolymerization select dimethyl-silicon abutment-tetramethyl-ring pentadienyl-tert-butylamino-dimethyl titanium, help and urge
Agent uses methylaluminoxane, and solvent is Isopar E, and monomer is ethylene and propylene, and polymerization experiment is continuous in series connection high temperature and pressure
It is carried out in solution system.Reaction kettle and pipeline triisobutyl aluminium and Isopar E wiring solution-forming are cleaned before experiment, to remove
Go water oxygen.Weigh up quantitative homopolymerization catalyst, catalyst for copolymerization, co-catalyst, nitrogen atmosphere protection under shift, respectively with
Isopar E wiring solution-forming is stored in respective storage tank, and solvent Isopar E also is stored in solvent storage tank.
Experimental procedure are as follows: open reaction kettle and pipeline oil bath, annular-pipe reactor temperature is increased to 120 DEG C, reacts kettle temperature
Degree is increased to 140 DEG C, and mixing speed is all set as 1000rpm；The inlet valve and outlet valve of two reactors are opened, 1~No. 5 height is opened
Chemical metering pump is pressed, five metering pumps continuously input in reaction kettle according to the flow velocity of setting, wherein propylene, propylene homo catalysis
Agent, co-catalyst, solvent continuously enter annular-pipe reactor, annular-pipe reactor discharging, catalyst for copolymerization, co-catalyst, ethylene, molten
Agent continuously enters reaction kettle, and reaction kettle pressure release discharges to obtain final product.Reacting kettle inner pressure passes through proportional valve control, works as ring
Pipe reactor pressure is stablized to be stablized after 20bar in 22bar, reacting kettle inner pressure, opens propylene intake valve, propylene passes through flow
Meter control constant speed enters two reaction kettles；Ethylene intake valve is opened, ethylene controls constant speed by flowmeter and enters reaction response kettle.System
After system reaches stable, annular-pipe reactor homopolymerization catalyst concentration is 4 μm of ol/L, cocatalyst concentration 10mmol/L, co-catalysis
The molar ratio of agent and major catalyst is 5000, and propene feed concentration 0.92mol/L, annular-pipe reactor temperature is controlled 120
DEG C, loop pressure control 22bar, material endless tube residence time be 8min；Reaction kettle catalyst for copolymerization concentration is 20 μ
The molar ratio of mol/L, cocatalyst concentration 20mmol/L, co-catalyst and major catalyst is 1000, ethylene feed concentrations
For 0.39mol/L, the raw materials components mole ratio example of propene feed concentration 0.80mol/L, propylene and ethylene are 2.05, temperature in the kettle control
In 20bar or so, residence time of the material in reaction kettle is 6min to system for pressure control in 140 DEG C, kettle.The object flowed continually out
Material after the washing for several times of a large amount of acidic ethanols, drain, and is dried in vacuo 8 hours or more at 60 DEG C by filtering.
1. tandem of table is catalyzed successive soln combined polymerization experimental result
Note: the POE production piece of the expression of ENGAGE 8150 DOW company
As shown in Table 1, the present invention is prepared for a series of pectination propylene based polyolefm thermoplasticity under high-temperature and high-pressure conditions
Elastomer, mechanical property show that polymer all shows the property of typical thermoplastic elastomer (TPE).It, should compared with production piece
Elastomer possesses higher fusing point (> 140 DEG C), shows more broader than POE using temperature.
Claims (8)
1. a kind of pectination propylene based polyolefm process for preparation of thermoplastic elastomer, which comprises the following steps:
(1) under the conditions of anhydrous and oxygen-free, propylene, propylene homo catalyst, co-catalyst and organic are added into first reactor
Solvent, polymerization reaction obtain polypropylene polymeric monomer.Polymerization temperature is about 60-300 DEG C, and polymerization pressure is about 0.1-10MPa.With anti-
The stereometer of organic solvent in kettle is answered, the propylene homo catalyst concn is 0.1~100 μm of ol/L, the co-catalysis
The molar ratio of agent and propylene homo catalyst is 50~10000:1, and the input concentration of propylene is 0.1~20mol/L；All materials
Residence time in the first reactor controls in 2~240min.The weight average molecular weight of obtained polypropylene polymeric monomer is
1000~50000g/mol, molecular weight distributing index are 1.0~5.0, and the control of terminal double bond ratio is polyacrylic 50% or more
Isotacticity or normality control are 50% or more.
(2) polymer solution that polymerization reaction obtains in first reactor enters in second reactor, under the conditions of anhydrous and oxygen-free,
Propylene, ethylene, catalyst for copolymerization, co-catalyst and organic solvent are added into second reactor, carries out ethylene/propene/poly- third
The ternary polymerization of alkene polymeric monomer, polymerization temperature are 60-300 DEG C, polymerization pressure 0.1-10MPa.With organic solvent in reaction kettle
Stereometer, the concentration of the catalyst for copolymerization is 0.1~100 μm of ol/L, and the catalyst for copolymerization is urged with propylene homo
The molar ratio of agent is 20:1~1:10, and the molar ratio of the co-catalyst and catalyst for copolymerization is 50~10000:1, described
Ethylene feed concentrations be 0.1~20mol/L, the raw materials components mole ratio of the propylene and ethylene is 0.1~25:1, all materials
Residence time in the second reactor controls in 2~240min.Obtained copolymer weight average molecular weight 20000~
500000g/mol, molecular weight distributing index 1.0~10.0, mole content 10~95% in main chain.
2. preparation method according to claim 1, which is characterized in that the propylene homo catalyst is single active center
Metallocene catalyst or post-metallocene catalyst, selected from the Asia rac- ethylene abutment double tetrahydroindenyl zirconium dichlorides, rac- dimethyl-silicon
Bridging-two (2- methylindenyl) zirconium dichloride, rac- dimethyl-silicon bridging-two (2- methyl 4-phenyl-indenyl) zirconium dichloride,
- two indenyl dimethyl hafnium of rac- dimethyl-silicon bridging, meso- diphenyl methyl bridging-cyclopentadienyl-fluorenyl-zirconium dichloride,
Bis- (dimethyl-silicon abutments)-(3,5- diisopropyl cyclopentadienyl group)-(4- isopropylcyclopentadienyl) zirconium dichloride, dimethyl
Silicon bridge base-fluorenyl-tert-butylamino-dimethyl titanium, bis- (3- trimethyl silicon substrate salicyl -3,5- difluorophenyl) titanium chloride.
3. preparation method according to claim 1, which is characterized in that the catalyst for copolymerization is the cyclopentadienyl of single active center
Metallic catalyst or post-metallocene catalyst, selected from bicyclic pentadiene dimethyl hafnium, double indenyl zirconium dimethyls, sub- ethylene abutment
Double tetrahydroindenyl zirconium dichlorides, dimethyl-silicon abutment-bis- indenyls, diphenyl carbon abutment-cyclopentadienyl group-tablet held before the breast by officials base zirconium dichloride, diformazan
Base silicon bridge base-tetramethyl-ring pentadienyl-tert-butylamino-dimethyl titanium, double tetrahydroindenyl zirconium dichlorides, bis- [2- (bis- uncles of 3', 5'-
Butyl phenyl)-indenyl] zirconium dichloride, bis- (2- methyl -4,5- pheny-indenylzirconium) zirconium dichlorides, the bis- benzene oxygen of bicyclic pentadiene -
Base zirconium, dimethyl-silicon abutment double tetrahydroindenyl zirconium dichlorides, diphenyl carbon abutment-cyclopentadienyl group-tablet held before the breast by officials base zirconium dichloride, diphenyl carbon
Abutment-cyclopentadienyl group-(2- dimethylamino-tablet held before the breast by officials base) zirconium dichloride, dimethyl-silicon abutment-tetramethyl-ring pentadienyl-tertiary fourth
Base amino-dimethyl titanium, dimethyl-silicon abutment -3- pyrrole radicals indenyl-tert-butylamino-dimethyl titanium, pentamethylcyclopentadiene
It is base-(2- phenylphenoxy)-titanium chloride, pentamethylcyclopentadiene base-(2,6- diisopropyl phenoxy group)-titanium chloride, double
(3- methyl salicylidene-phenyl-pentafluoride imido grpup) titanium chloride, bis- (salicylidene-phenyl imido) titanium chloride, dimethyl-silicon
Abutment -3- pyrrole radicals indenyl-tert-butylamino-dimethyl titanium, [N- (3,5- di-tert-butyl Salicylidene) -2- diphenylphosphoryl group
Benzene imines] titanium trichloride, (tri- hydrogen -8- diphenylphosphoryl group of 2,3,4--quinolyl) tribenzyl zirconium.
4. preparation method according to claim 1, which is characterized in that the co-catalyst is selected from methylaluminoxane, changes
Property methylaluminoxane, three (pentafluorophenyl group) boron compounds, triisobutyl aluminium, triethyl aluminum, trimethyl aluminium.
5. preparation method according to claim 1, which is characterized in that the organic solvent is with 4~10 carbon originals
Linear paraffin, isoparaffin, cycloalkane or the aralkyl hydrocarbon of son.
6. preparation method according to claim 5, which is characterized in that the preferred pentane of the organic solvent, isopentane,
N-hexane, hexamethylene, normal heptane, isoheptane, normal octane, isooctane, n-decane, isomeric alkane hydrocarbon ils, toluene, dimethylbenzene.
7. preparation method according to claim 1, which is characterized in that polypropylene polymeric monomer terminal double bond made from step 1
Ratio preferably 80% or more；Polyacrylic isotacticity or normality preferably 80% or more.
8. preparation method according to claim 1, which is characterized in that polymer fracture elongation made from step 2 is greater than
100%, breaking strength is greater than 1Mpa.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111635494A (en) * | 2020-06-19 | 2020-09-08 | 浙江大学衢州研究院 | Preparation method of comb-shaped propenyl olefin polymer |
| CN114539477A (en) * | 2022-01-05 | 2022-05-27 | 浙江大学衢州研究院 | Preparation method of ethylene propylene diene monomer |
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|---|---|---|---|---|
| WO1994021692A1 (en) * | 1993-03-18 | 1994-09-29 | Neste Oy | Ethylene-propylene copolymer and method for manufacturing the same |
| CN101331163A (en) * | 2005-09-15 | 2008-12-24 | 陶氏环球技术公司 | Catalytic olefin block copolymers via polymerizable shuttling agent |
| CN107949589A (en) * | 2015-09-14 | 2018-04-20 | 埃克森美孚化学专利公司 | It can be used as the atactic polypropylene comb block polyolefin of the modifying agent in polyolefin and hydrocarbon |
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2018
- 2018-09-29 CN CN201811148679.3A patent/CN109456445B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994021692A1 (en) * | 1993-03-18 | 1994-09-29 | Neste Oy | Ethylene-propylene copolymer and method for manufacturing the same |
| CN101331163A (en) * | 2005-09-15 | 2008-12-24 | 陶氏环球技术公司 | Catalytic olefin block copolymers via polymerizable shuttling agent |
| CN107949589A (en) * | 2015-09-14 | 2018-04-20 | 埃克森美孚化学专利公司 | It can be used as the atactic polypropylene comb block polyolefin of the modifying agent in polyolefin and hydrocarbon |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111635494A (en) * | 2020-06-19 | 2020-09-08 | 浙江大学衢州研究院 | Preparation method of comb-shaped propenyl olefin polymer |
| CN114539477A (en) * | 2022-01-05 | 2022-05-27 | 浙江大学衢州研究院 | Preparation method of ethylene propylene diene monomer |
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