CN105330955B - A kind of preparation method of impact polypropylene - Google Patents
A kind of preparation method of impact polypropylene Download PDFInfo
- Publication number
- CN105330955B CN105330955B CN201410304945.2A CN201410304945A CN105330955B CN 105330955 B CN105330955 B CN 105330955B CN 201410304945 A CN201410304945 A CN 201410304945A CN 105330955 B CN105330955 B CN 105330955B
- Authority
- CN
- China
- Prior art keywords
- propylene
- reaction
- phase
- gas
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a kind of preparation method of impact polypropylene, it is included in the presence of ziegler natta catalyst and carries out propylene homo reaction, Noblen is obtained, the copolymerization that nitrous oxide carries out ethene and propylene is then added, obtains the impact polypropylene of high ethylene contents.The nitrous oxide coordinates with ziegler natta catalyst, effectively improve the ethene reactivity ratio in Propylene polymerization reaction, vinyl monomer concentration in reducing gas phase composition while guarantee product high ethylene contents, reduces energy consumption, meet existing condensation/cooling device removes heat energy power.
Description
Technical field
The present invention relates to a kind of preparation method of impact polypropylene, more particularly to a kind of impact polypropylene of high ethylene contents
Preparation method, belong to polypropylene production technical field.
Background technology
Impact polypropylene has the rigidity of Noblen and the impact resistance of EP rubbers component concurrently, has strong and unyielding well
Balance, is widely used to the fields such as automobile, household electrical appliance and injection moulded containers.Wherein, rubber-phase content is higher, the anti-impact of product
It is better to hit performance, and ethylene contents are higher in rubber phase, the stress-whitening resistance of product can be better, therefore, carries high impact poly
Ethylene contents in propylene turn into the target that researcher pursues.
But in actual production process, when the ethylene contents in polymerization system reach in the production capacity of existing polymerization technique
In limited time, the ethylene contents in the content of EP rubbers component and rubber phase can not be improved further, the impact resistance of product and
Stress-whitening resistance can be also limited, and surmounted art methods and obtained having the impact polypropylene of higher ethylene contents will
With more application prospect and the market competitiveness.
It is prepared by the impact polypropylene generally use multistep polymerization method of high ethylene contents.Propylene is carried out in first reactor
Homopolymerization obtains acrylic polymers, the copolymerization that next reactor carries out propylene and ethene is then sent to, in propylene polymerization
Polymer of the generation based on ethylene-propylene random copolymer in the hole of composition granule.
At present, most impact polypropylenes uses ethene as comonomer, and propylene-ethylene copolyreaction exists
Carried out in Gas-phase reactor.And the Gas-phase reactor of the polymerization technique such as Unipol, Novolen, Horizone and Innovene
It is cooling/condensation by circulating air, and propylene liguid is sprayed to bed, by propylene liguid gasification heat absorption come the system of removing
Reaction heat.When producing high impact resistance polypropylene product, to improve the ethylene contents in product, ethene can be accordingly improved in gas phase
Concentration in composition, but ethene is a kind of fixed gas, and the addition of a large amount of vinyl monomers can be greatly reduced the dew point of circulating air, difficult
With cooling/condensation, cause heat exchanger duty rise and heat exchange efficiency low, and then cause device capbility to reduce.Therefore, production is high
During ethylene contents impact polypropylene product polyplant can only be made to be operated under poor efficiency；And ensure the normal production of polyplant
During efficiency, the ethylene contents of product can not be but improved, product grade is limited, and greatly affected the economic benefit of enterprise.
Solve three kinds of methods of this problem generally use：First method is to improve the thermic load of circulating air heat exchanger, example
As used the heat exchanger with high heat load, or a heat exchanger of being connected after existing heat exchanger.But this scheme will increase expense
With investment, and without the energy consumption level for reducing device.Second method (is higher than by improving the reaction temperature of copolymerization stage
80 DEG C) exchange capability of heat of circulating air heat exchanger is improved, such as Chinese patent CN1421468A, CN1887917A and CN1887918A
Disclosed method, by increasing the temperature difference between the cold and hot medium of circulating air heat exchanger, and then effectively improve the heat exchange effect of heat exchanger
Rate.But the drawbacks of this method, is, the rapid decay of conventional Zigler-Natta catalyst activity at a temperature of higher than 80 DEG C,
Copolyreaction is caused to be difficult to, the ethylene contents and rubber-phase content of product are difficult to the requirement that touches the mark.The third method is
Extend the copolyreaction time, change the composition of catalyst system, Yi Jizhuan as mentioned in patent US0092656 and US5990251
Mentioned in sharp US0152483 and CN1189505 and add accelerative activator in the copolyreaction stage, ensure catalyst in copolymerization stage
Still there is sufficiently high polymerization activity.But the method can only improve propylene-ethylene copolymers rubber phase component as a rule
Content, due to the uncertainty on ethene and the influence of propylene monomer reactivity ratio, cause ethylene contents in rubber phase or most
The ethylene contents of finished product are not greatly improved or even declined, and influence the impact resistance and stress-whitening resistance energy of product.Therefore,
Need to find a kind of method for improving ethene reactivity ratio, make the propylene-ethylene gas-phase copolymerization stage in relatively low vinyl monomer concentration
Under can still obtain the impact polypropylene product with high ethylene contents, while do not increase the improvement cost of device, reduce energy consumption, open up
The ability of the wide process unit production premium quality product trade mark.
The content of the invention
In order to overcome prior art when preparing high ethylene contents impact polypropylene, copolymerization stage on-condensible gas concentration height is made
Into circulating air efficiency of heat exchanger is low, device capbility decline, high energy consumption, high plant modification cost the defects of, mesh of the invention
Be to provide a kind of preparation method of impact polypropylene, propylene and ethene is polymerize under relatively low vinyl monomer concentration and obtain height
The impact polypropylene of ethylene contents.Cause that circulating air efficiency of heat exchanger is low, dress this method avoid on-condensible gas concentration height
The problems such as putting production capacity decline, high energy consumption, high plant modification cost.
The invention provides a kind of preparation method of impact polypropylene, exists in ziegler natta catalyst and nitrous oxide
Under, polymerisation is carried out as raw material using propylene and ethene, the polymerisation is entered in the polymer reactor of at least two series connection
OK.Specifically, the described method comprises the following steps：
Step 1: carrying out propylene homo reaction in the presence of ziegler natta catalyst, Noblen is obtained；
Step 2: nitrous oxide is added in the presence of the Noblen that step 1 obtains carries out being total to for ethene and propylene
Polymerisation, obtain the impact polypropylene of high ethylene contents；
Wherein, the step 1 is carried out under propylene gas-phase polymerization or the reaction condition of liquid phase polymerization, and the step 2 exists
Carried out under the reaction condition of Ethylene-propylene Gas-phase Copolymerization.
In the present invention, the propylene homo reaction of step 1 is carried out in the first polymer reactor, and to polymer reactor
Form does not have particular/special requirement, gas phase or Liquid-phase reactor.Optional Liquid-phase reactor has annular-pipe reactor, vertical stirred tank
Reactor, optional Gas-phase reactor have fluidized-bed reactor, horizontal type agitated bed reactor and vertical mixing bed reactor.
The ethylene-propylene copolymer reaction of step 2 is carried out in the second polymer reactor.Second polymer reactor is
Gas-phase reactor, preferably horizontal retort Gas-phase reactor.In one particular embodiment of the present invention, described horizontal retort gas phase
Reactor carries horizontal type agitating shaft, and speed of agitator is 10-150 revs/min, stirring vane from T-shaped, rectangle, oblique oar, gate,
Wedge shape or its combination.The horizontal retort Gas-phase reactor removes heat using chilling liquid, i.e., by cooling/condensation of circulating air, and
Propylene liguid is sprayed to bed, is gasified by propylene liguid and absorbs heat to remove system response heat.The type reactor follows
The concentration of on-condensible gas is very sensitive during ring air cooling/condensing plant forms to gas, and excessive concentration will cause equipment to remove heat energy
The problems such as power deficiency, operating load rise, energy consumption increase and production capacity decline.Do not coagulated if ethene reactivity ratio can be improved and reduced
Gas concentration, the operating condition of the type reactor can be effectively improved.
In one particular embodiment of the present invention, by nitrous oxide and inert component (such as nitrogen for being not involved in polymerisation
Gas, argon gas), or carry out (such as ethene, propylene) with reactor feed gas and mix, pass through the feedstock pipeline of the second polymer reactor
Or circulating air pipeline is added in polymerization reaction system.According to the present invention, the addition of nitrous oxide can be according to the ethene in product
Content requirement is controlled by gas flowmeter and electronic regulated valve, and passes through on-line analysis tester (such as gas-chromatography)
Gas composition in the second polymer reactor of monitoring in real time.Concentration of the nitrous oxide in the second polymer reactor is
0.01-10ppm, preferably 0.01-5ppm, most preferably 1-3ppm.
In step 1, the propylene gas phase or liquid phase homopolymerization are preferably carried out under the following conditions：Temperature is 50-
100 DEG C, preferably 60-90 DEG C；Pressure is 1-6MPa, preferably 2-5MPa；Polymerization time is 20-120 minutes, preferably 30-
90 minutes.
In step 2, the Ethylene-propylene Gas-phase Copolymerization reaction is preferably carried out under the following conditions：Temperature is 50-90
DEG C, preferably 60-80 DEG C；Pressure is 1-5MPa, preferably 2-4MPa；Polymerization time is 20-120 minutes, and preferably 30-90 divides
Clock.
In the step one and step 2 of the present invention, the pressure of appearance is meter pressure.
In step 1, such as it is not particularly limited, the additional proportion of the ziegler natta catalyst and propylene, Yi Jiqing
The mol ratio of gas/propylene is this area conventional selection, is had no special requirements.The throwing of hydrogen and propylene under the conditions of liquid-phase polymerization
Expect that ratio is 0-2000ppm；Under the conditions of gas phase polymerization, the mol ratio of hydrogen/propylene is 0-0.03 in gas phase composition.
In step 2, such as it is not particularly limited, the addition of the ethene and propylene, both additional proportions, and instead
The mol ratio for answering hydrogen/propylene in gas phase is this area conventional selection.It is preferred that the mol ratio of hydrogen/propylene is in reaction gas phase
0-0.03。
In the method for the invention, metallocene (Ziegler-Natta) catalyst used is largely disclosed, excellent
Choosing can prepare the Noblen that isotactic index is more than 95% using the catalyst with high stereoselective.Institute
The Ziegler-Natta catalyst stated includes：
1) ingredient of solid catalyst of titaniferous；
2) alkyl aluminum compound；And
3) optional external donor compound.
Wherein, the ingredient of solid catalyst of the titaniferous, the alkyl aluminum compound and the external donor compound
Mol ratio be 1: 5-500: 0-500, preferably 1: 25-100: 25-100.
Component 1 in the catalyst that the present invention uses) titaniferous ingredient of solid catalyst, be by titanium compound, magnesium chemical combination
Thing and the catalytic product of internal electron donor compound.It is specific be documented in Chinese patent CN85100997, CN93102795.0,
CN98126383.6、CN98111/80.5、CN98126385.2、CN99125566.6、CN9912556/.4、
In CN00109216.2, CN02100900.7, CN201210426370.2.Described catalyst can be used directly, can also
Added after pre- complexing and/or prepolymerization.
Component 2 in the catalyst that the present invention uses) formula of alkyl aluminum compound is
AlR16 nX3-n (I)。
R in formula (VI)16The alkyl for being 1-20 for hydrogen or carbon number, X are halogen, and n is the number of 1 ＜ n≤3；It is specific optional
From triethyl aluminum, tri-propyl aluminum, three n-butylaluminums, triisobutyl aluminium, tri-n-octylaluminium, triisobutyl aluminium, a hydrogen diethyl aluminum,
In one hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium, ethyl aluminum dichloride at least
One kind, preferably triethyl aluminum or triisobutyl aluminium.
Component 3 in the catalyst that the present invention uses) external donor compound is siliconated shown in logical formula (II)
Compound,
R′pR"qSi(OR"′)4-p-q (II)
In formula (II), R ' and R " are identical or different, and it is 1-20's to be each independently selected from halogen, hydrogen atom, carbon number
In the haloalkyl that the aryl and carbon number that cycloalkyl that alkyl, carbon number are 3-20, carbon number are 6-20 are 1-20
One kind；R " ' be carbon number be 1-20 alkyl, carbon number be 3-20 cycloalkyl, carbon number be 6-20 aryl
The one kind in haloalkyl for being 1-20 with carbon number；P and q is respectively 0-3 integer, and p+q ＜ 4.
The external electron donor can be trimethylmethoxysilane, diisopropyl dimethoxy silane, diisobutyl two
Methoxy silane, isopropyl butyldimethoxysilane, di-t-butyl dimethoxysilane, tertbutyl methyl dimethoxy silicon
Alkane, t-butylethyl dimethoxysilane, tert-butyl group propyldimethoxy-silane, ter /-butylisopropyl dimethoxysilane, ring
Hexyl methyl dimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclopenta first
Base dimethoxysilane, cyclopentyl ethyl dimethoxysilane, dicyclopentyl dimethoxyl silane, cyclopentyl cyclohexyl dimethoxy
Base silane, double (2- methylcyclopentyls) dimethoxysilanes, dimethoxydiphenylsilane, diphenyl diethoxy silane, two
Phenyidimethoxysilane, diphenyl diethoxy silane, phenyl triethoxysilane, MTMS, methyl three
Ethoxysilane, ethyl trimethoxy silane, propyl trimethoxy silicane, isopropyltri-methoxysilane, butyl trimethoxy
Silane, butyl triethoxysilane, trimethoxysilane, amyltrimethoxysilane, isopentyl trimethoxy silane,
Cyclopentyl-trimethoxy-silane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, positive third
In base trimethoxy silane, vinyltrimethoxy silane, tetramethoxy-silicane, tetraethoxysilane, four butoxy silanes
It is one or more；It is preferred that dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, diisobutyl dimethoxy silicon
At least one of alkane, Cyclohexyl Methyl Dimethoxysilane；Further preferred diisopropyl dimethoxy silane.
Present invention also offers the impact polypropylene for the high ethylene contents being prepared by the above method, the anti-impact is gathered
In propylene) total ethylene contents are 8-30wt%, rubber-phase content 20-50wt%, the ethylene contents in preferred rubber phase are 30-
60wt%.
The nitrous oxide that the present invention adds in step 2 coordinates with ziegler natta catalyst, effectively improves step 2
Ethene reactivity ratio in Propylene polymerization reaction, the vinyl monomer in reducing gas phase composition while guarantee product high ethylene contents
Concentration, energy consumption is reduced, meet existing condensation/cooling device removes heat energy power.
In addition, the nitrous oxide has oxidability under the high temperature conditions, can be by ziegler natta catalyst
Ti3+It is oxidized to Ti4+, amount of activated center is inactivated, oxygen, carbon monoxide, water etc. can be replaced to kill agent living, control gas-phase copolymerization
The course of reaction in stage, prevent implode and viscous kettle phenomenon.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The present invention will be described in detail by way of examples below.
The relevant data of polymer are obtained by following test method in embodiment：
(1) ethylene contents (RCC2) and rubber-phase content (RC) in total ethylene contents (TOTC2), rubber phase：Thermo
Nicolet200 type infrared spectrum analysers are in 720-730cm-1The peak area at place corresponds to total ethylene contents TOTC2；730-740cm-1Place
Peak area correspond to free state ethylene contents, 720cm-1、727cm-1、729cm-1The peak area at place is correspondingly copolymerized state ethylene contents,
The ratio of ethylene contents of the free state with being copolymerized state is ethylene contents RCC2 in rubber phase.
Rubber-phase content (RC)：According to formulaCalculated.
(2) bending modulus：Measured according to ASTM D790-97.
(3) tensile strength：Measured according to ASTM D638-00.
(4) hit intensity in Izod：Measured according to ASTM D256-00.
(5) Ti content in catalyst is tested with 721 spectrophotometers.
(6) grain size of alkoxyl magnesium and catalyst, size distribution are swashed with Malvern Mastersizer TM2000
Optical diffraction method measures, and n-hexane is dispersant (wherein, SPAN=(D90-D10)/D50).
(7) measure of the m values in carrier：0.1 gram of carrier is taken, adds 10mL1.2mol/L aqueous hydrochloric acid solutions, concussion 24 is small
When make its decomposition, ethanol therein and 2-Ethylhexyl Alcohol are quantified using gas-chromatography, m values are then calculated as follows：
In formula, w1 is 2-Ethylhexyl Alcohol quality, and w2 is ethanol quality.
(8) in catalyst component for olefin polymerization internal electron donor content be measured using Waters600E liquid chromatograies or
Gas Chromatographic Determination.
(9) chilling liquid spray flux is the data read from polyplant on chilling nozzle for liquid flowmeter.
Preparation example
This preparation example is used for preparing the ingredient of solid catalyst of the titaniferous in Ziegler-Natta catalyst.
After the 16L voltage-resistant reactors with agitator are sufficiently displaced from nitrogen, added into reactor 10L ethanol,
300mL2- ethyl hexanols, 11.2g iodine, 8g magnesium chlorides and 640g magnesium powders.Stirring makes system back flow reaction simultaneously, until there is no
Untill hydrogen is discharged.Stop reaction, product is washed with 3L ethanol, filtered, is dried, obtains alkoxyl magnesium carrier.It is described
Alkoxyl magnesium carrier D50=30.2um, Span=0.81, m=0.015.Take above-mentioned alkoxyl magnesium carrier 650g and toluene
3250mL is configured to suspension.In the pressure-resistant reactors of 16L of displacement are repeated by high pure nitrogen, toluene 2600mL and four is added
Titanium chloride 3900mL, 80 DEG C are warming up to, then added the suspension prepared in kettle, constant temperature 1 hour, add phthalic acid
Diethylester 130mL, 110 DEG C are to slowly warm up to, constant temperature 2 hours, press filtration obtains solid content.Gained solid content add toluene 5070mL and
Titanium tetrachloride 3380mL mixed liquor is processed as 3 times in 110 DEG C of stir process 1 hour.Repeat the solid that press filtration obtains and use oneself
Alkane washs 4 times, each 6000mL, press filtration, drying, produces the ingredient of solid catalyst of titaniferous.The solid catalyst of gained titaniferous
Titanium atom content 2.4wt% in component, diethyl phthalate content 10.5wt%.
Embodiment 1
For the present embodiment for illustrating in the method for preparing high ethylene contents impact polypropylene, nitrous oxide can improve ethene
Reactivity ratio.
1) raw material
Using the ziegler natta catalyst obtained in preparation example as major catalyst；Triethyl aluminum is co-catalyst；Two
Isopropyl dimethoxysilane (DIPDMS) is external electron donor；Propylene, ethene and hydrogen are polymer grade, after removing water, oxygen
Use；Hexane uses after dehydration；Nitrous oxide and nitrogen are made into mixed gas according to 1: 25 mol ratio and used.
2) experimental rig
Using the polymerization technique of two horizontal retort Gas-phase reactor series connection.0.2 cubic metre of horizontal retort Gas-phase reactor volume,
Agitating paddle is T-shaped oblique blade, and angle of inclination is 10 degree, and mixing speed is 100 revs/min.
3) process is tested
The gas-phase propene homopolymerization of (1) step：Major catalyst, triethyl aluminum, outer is added in the first horizontal retort Gas-phase reactor
Electron donor and propylene carry out polymerisation.Wherein, major catalyst, triethyl aluminum, the inlet amount of external electron donor are respectively
0.9g/hr, 0.072mol/hr, 0.012mol/hr, Al/Si (mol/mol)=8.59；Propylene feed amount is 15kg/hr；Reaction
Hydrogen/propylene molar ratio is 0.033 in gas phase；The temperature of polymerisation is 85 DEG C, pressure 2.5MPa, and the time is 60 minutes,
Obtain propylene homo product；
(2) step propylene and ethene gas-phase copolymerization：In the second horizontal retort Gas-phase reactor, obtained in (1) step third
In the presence of polyamino alkenyl product, the mixed gas of nitrous oxide and nitrogen, and unstripped gas second are added by feedstock pipeline
Alkene and propylene carry out polymerisation.Ethene and propylene feed amount are respectively 3.6kg/hr, 15kg/hr, and ethylene/propene mol ratio is
0.45；It is 0.039 to react hydrogen/propylene molar ratio in gas phase；The temperature of polymerisation is 66 DEG C, pressure 2.4MPa, the time
For 80 minutes, final polymerizate, i.e. impact polypropylene product are obtained.Concrete technology condition is shown in Table 1.
4) result of the test
The long run test of 48 hours has been carried out according to above-mentioned condition, device stable operation, the polymer that reaction obtains has been entered
Row analysis test, is as a result listed in table 1.
It is sub- except being aoxidized in (2) step propylene and ethene gas phase polymerization process of experiment process in embodiment 2 and embodiment 3
The addition of nitrogen is different outer, and other conditions are shown in Table 1 with embodiment 1, concrete technology condition and result of the test.
Comparative example 1
When this comparative example is used for illustrating that vinyl monomer concentration is identical in gas phase composition, nitrous oxide, anti-impact poly- third are not added
Ethylene contents will reduce in alkene product.
In addition to nitrous oxide is not added in (2) step propylene and ethene gas phase polymerization process of experiment process, other conditions
With embodiment 1, concrete technology condition and result of the test are shown in Table 1.
Comparative example 2
When this comparative example is used for illustrating the impact polypropylene product for obtaining identical ethylene contents, nitrous oxide, gas are not added
Vinyl monomer concentration in phase composition will increase.
Except nitrous oxide is not added in (2) step propylene and ethene gas phase polymerization process of experiment process, carry as needed
High ethylene, propylene ratio is outer, and other conditions are shown in Table 1 with embodiment 1, concrete technology condition and result of the test.
As can be seen from Table 1, it is competing to ethene mainly to reflect nitrous oxide addition for the test data of embodiment 1,2 and 3
The influence of poly- rate.In second Gas-phase reactor in the case of ethene and propylene molar ratio identical, nitrous oxide is gradually increased by 1ppm
3ppm is added to, ethylene contents, the rubber-phase content of its product, and ethylene contents in rubber phase also gradually rise therewith, say
Bright nitrous oxide has obvious facilitation to improving ethene reactivity ratio.
The test data of embodiment 1 and comparative example 1 mainly reflects influence of the nitrous oxide to ethene reactivity ratio.Second gas
In phase reaction device in the case of ethene and propylene molar ratio identical, embodiment 1 adds nitrous oxide, and the ethene of its product contains
Ethylene contents in amount, rubber-phase content, and rubber phase are above the comparative example 1 for not adding nitrous oxide, illustrate nitrous oxide
There is obvious facilitation to improving ethene reactivity ratio.Meanwhile the product of embodiment 1 ethylene contents improve in the case of,
Tensile strength and bending modulus are not decreased obviously but, maintain good rigidity.
The test data of embodiment 1 and comparative example 2 mainly reflects nitrous oxide to ethene reactivity ratio and plant energy consumption
Influence.In the case that ethylene contents are kept quite in the product of embodiment 1 and comparative example 2, the nitrous oxide of the addition of embodiment 1
Improve ethene reactivity ratio, ethene and the propylene molar ratio in its gas phase composition are reduced to 0.44, and comparative example 2 up to
0.61.The increase of vinyl monomer concentration in comparative example 2, condensation/cooling device load increase of device certainly will be made, be embodied in
The chilling flow quantity of second Gas-phase reactor of comparative example 2 is apparently higher than embodiment 1.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of preparation method of impact polypropylene, including：
Step 1: carrying out propylene homo reaction in the presence of ziegler natta catalyst, Noblen is obtained；
Step 2: the combined polymerization that nitrous oxide carries out ethene and propylene is added in the presence of the Noblen that step 1 obtains
Reaction, the impact polypropylene of high ethylene contents is obtained, total ethylene contents are 8-30wt% in the impact polypropylene, and rubber mutually contains
Measure as 20-50wt%；
Concentration of the nitrous oxide in the second polymer reactor is 1-3ppm；
The ziegler natta catalyst includes：
1) ingredient of solid catalyst of titaniferous；
2) alkyl aluminum compound；And
3) optional external donor compound.
2. according to the method for claim 1, it is characterised in that it is carried out in the polymer reactor of at least two series connection,
Propylene homo reaction is carried out in first polymer reactor, ethylene propylene copolymer reaction is carried out in the second polymer reactor.
3. according to the method for claim 2, it is characterised in that the nitrous oxide and the inertia group for being not involved in polymerisation
Point, or mixed with reaction raw materials gas, added by the feedstock pipeline or circulating air pipeline of the second polymer reactor.
4. according to the method for claim 1, it is characterised in that the step 1 is in propylene gas-phase polymerization or liquid phase polymerization
Carried out under reaction condition, the step 2 is carried out under the reaction condition of Ethylene-propylene Gas-phase Copolymerization.
5. according to the method for claim 4, it is characterised in that in step 1, step 1 propylene gas phase or liquid phase polymerization
Reaction temperature be 50-100 DEG C；Pressure is 1-6MPa；Polymerization time is 20-120 minutes.
6. according to the method for claim 5, it is characterised in that in step 1, step 1 propylene gas phase or liquid phase polymerization
Reaction temperature be 60-90 DEG C；Pressure is 2-5MPa；Polymerization time is 30-90 minutes.
7. according to the method for claim 4, it is characterised in that the reaction temperature of step 2 Ethylene-propylene Gas-phase Copolymerization is
50-90℃；Pressure is 1-5MPa；Polymerization time is 20-120 minutes.
8. according to the method for claim 7, it is characterised in that the reaction temperature of step 2 Ethylene-propylene Gas-phase Copolymerization is
60-80℃；Pressure is 2-4MPa；Polymerization time is 30-90 minutes.
9. according to the method for claim 1, it is characterised in that the ingredient of solid catalyst of the titaniferous, the alkyl aluminum
Compound and the mol ratio of the external donor compound are 1:5-500:0-500.
10. according to the method for claim 9, it is characterised in that the ingredient of solid catalyst of the titaniferous, the alkyl aluminum
Compound and the mol ratio of the external donor compound are 1:25-100:25-100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410304945.2A CN105330955B (en) | 2014-06-30 | 2014-06-30 | A kind of preparation method of impact polypropylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410304945.2A CN105330955B (en) | 2014-06-30 | 2014-06-30 | A kind of preparation method of impact polypropylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105330955A CN105330955A (en) | 2016-02-17 |
| CN105330955B true CN105330955B (en) | 2018-01-23 |
Family
ID=55281735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410304945.2A Active CN105330955B (en) | 2014-06-30 | 2014-06-30 | A kind of preparation method of impact polypropylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105330955B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110551242B (en) * | 2018-05-31 | 2022-03-29 | 中国石油天然气股份有限公司 | Impact-resistant co-polypropylene and preparation method thereof |
| CN111269491B (en) * | 2020-03-24 | 2021-06-22 | 浙江大学 | A kind of olefin gas phase polymerization method |
| CN111875726B (en) * | 2020-08-12 | 2023-02-24 | 上海赛科石油化工有限责任公司 | Polypropylene production operation control method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4234716A (en) * | 1977-09-12 | 1980-11-18 | Solvay & Cie. | Process for the separation of polyolefins manufactured at low pressure |
| CN1205726A (en) * | 1995-11-24 | 1999-01-20 | 智索公司 | Propylene compsn, process for preparing same, polypropylene compsn., and molded articles |
| CN1324369A (en) * | 1998-10-27 | 2001-11-28 | 伊斯曼化学公司 | Process for the polymerization of olefins |
| EP1207170A1 (en) * | 2000-11-20 | 2002-05-22 | BP Chemicals S.N.C. | Process for the continuous gas-phase (co-)polymerisation of olefins in a fluidised bed reactor |
| CN1367797A (en) * | 1999-08-31 | 2002-09-04 | 伊斯曼化学公司 | Process for producing polyolefins |
| CN102585352A (en) * | 2011-01-12 | 2012-07-18 | 中国石油化工股份有限公司 | Stress whitening-resistant and impact-resistant polypropylene composite |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006107373A1 (en) * | 2005-03-31 | 2006-10-12 | Exxonmobil Chemical Patents Inc. | Processes for producing high density polyethylene |
-
2014
- 2014-06-30 CN CN201410304945.2A patent/CN105330955B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4234716A (en) * | 1977-09-12 | 1980-11-18 | Solvay & Cie. | Process for the separation of polyolefins manufactured at low pressure |
| CN1205726A (en) * | 1995-11-24 | 1999-01-20 | 智索公司 | Propylene compsn, process for preparing same, polypropylene compsn., and molded articles |
| CN1324369A (en) * | 1998-10-27 | 2001-11-28 | 伊斯曼化学公司 | Process for the polymerization of olefins |
| CN1367797A (en) * | 1999-08-31 | 2002-09-04 | 伊斯曼化学公司 | Process for producing polyolefins |
| EP1207170A1 (en) * | 2000-11-20 | 2002-05-22 | BP Chemicals S.N.C. | Process for the continuous gas-phase (co-)polymerisation of olefins in a fluidised bed reactor |
| CN102585352A (en) * | 2011-01-12 | 2012-07-18 | 中国石油化工股份有限公司 | Stress whitening-resistant and impact-resistant polypropylene composite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105330955A (en) | 2016-02-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101484480B (en) | Process for preparing a catalyst component for propylene polymerization | |
| CN106164111B (en) | Catalyst system for olefinic polymerization | |
| CN105849179B (en) | Heterophasic propylene copolymers | |
| CN105622808B (en) | A kind of production method of impact polypropylene | |
| CN102268160B (en) | Polybutene alloy material and preparation method thereof | |
| JPS5950246B2 (en) | Production method of olefin copolymer for molding | |
| CN105934449A (en) | Catalyst system for polymerization of olefin | |
| EP3331923B1 (en) | Process for the polymerization of olefins | |
| WO2009050045A2 (en) | Process for the preparation of high fluidity propylene polymers | |
| CN1008907B (en) | Catalyst component catalyst for olefin polymerization and polymerization process | |
| KR101742714B1 (en) | Method for preparation of propylene polymer | |
| BR112016013799B1 (en) | PRO-CATALYST FOR THE POLYMERIZATION OF AN OLEFIN, ITS PREPARATION PROCESS, USE OF FORMULA X BENZAMIDE AND POLYOLEFIN PREPARATION PROCESS | |
| CN110016093A (en) | Ingredient of solid catalyst and catalyst system and olefine polymerizing process for olefinic polymerization | |
| CN108349873A (en) | The purposes of the synthesis of substituted amido benzoic acid ester compounds, the compound obtained and the compound as the internal electron donor without phthalic acid ester for olefin polymerization | |
| CN108699283A (en) | Composition comprising a heterophasic propylene copolymer | |
| CN105330955B (en) | A kind of preparation method of impact polypropylene | |
| CN104558336B (en) | A kind of propylene copolymer and preparation method thereof | |
| CN104558300B (en) | A kind of polyacrylic method of production and thus obtained polypropylene | |
| CN105218721B (en) | A kind of preparation method of impact polypropylene | |
| JPS5812888B2 (en) | Method for manufacturing polyolefin | |
| CN104031183B (en) | A kind of for the catalytic component of olefinic polymerization, preparation method and application thereof | |
| CN104558337B (en) | A kind of propylene copolymer and preparation method thereof | |
| JPH0344564B2 (en) | ||
| CN103788258B (en) | A kind of polymerization of propylene | |
| CN113248637A (en) | External electron donor compound, olefin polymerization catalyst and application thereof, and polyolefin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |