CN105330955A - Preparation method of impact-resistant polypropylene - Google Patents
Preparation method of impact-resistant polypropylene Download PDFInfo
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Abstract
The invention relates to a preparation method of impact-resistant polypropylene. The method comprises the following steps: performing a propylene homopolymerization reaction under existence of a ziegler-natta catalyst, then adding nitrous oxide for a copolymerization reaction of ethylene and propylene to obtain the impact-resistant polypropylene with high ethylene content. Cooperation of the nitrous oxide and the ziegler-natta catalyst can effectively increase ethylene reactivity ratio in the ethylene propylene copolymerization reaction, high ethylene content of the product is guaranteed, at the same time, ethylene monomer concentration in gas phase composition is reduced, production energy consumption is reduced, and heat removing capability of a current condensation/cooling device can be satisfied.
Description
Technical field
The present invention relates to a kind of preparation method of impact polypropylene, particularly a kind of preparation method of impact polypropylene of high ethylene content, belongs to polypropylene production technical field.
Background technology
Impact polypropylene has the rigidity of alfon and the shock resistance of ethylene-propylene rubber(EPR) component concurrently, has good rigidity-toughness balanced, has been widely used in the fields such as automobile, household electrical appliance and injection moulded containers.Wherein, rubber-phase content is higher, and the shock resistance of product is better, and in rubber phase, ethylene content is higher, and the stress-whitening resistance of product can be better, and therefore, the ethylene content improved in impact polypropylene becomes the target that researchist pursues.
But in actual production process, when the throughput that the ethylene content in polymerization system reaches existing polymerization technique is prescribed a time limit, ethylene content in the content of ethylene-propylene rubber(EPR) component and rubber phase all cannot improve further, the shock resistance of product and stress-whitening resistance can also will be restricted, and surmount the impact polypropylene that art methods obtains having higher ethylene content and will have more application prospect and the market competitiveness.
The impact polypropylene of high ethylene content adopts multistep polymerization method to prepare usually.In the first reactor, carry out propylene homo obtain propene polymer, be then transported to the copolymerization that next reactor carries out propylene and ethene, in the hole of propylene polymerization composition granule, generate the polymkeric substance based on ethylene-propylene random copolymer.
At present, the impact polypropylene of the overwhelming majority all uses ethene as comonomer, and propylene-ethylene copolyreaction is carried out in Gas-phase reactor.And the Gas-phase reactor of the polymerization techniques such as Unipol, Novolen, Horizone and Innovene is the cooling/condensation by circulation gas, and spray propylene liquid to bed, remove system response heat by propylene liquid gasification heat absorption.When producing high impact resistance polypropylene product, for improving the ethylene content in product, the concentration of the corresponding raising ethene of meeting in gas phase composition, but ethene is a kind of non-condensable gas, the membership that adds of a large amount of vinyl monomer makes the dew point of circulation gas significantly reduce, be difficult to cooling/condensation, cause heat exchanger duty rising and heat exchange efficiency lowly, and then cause device capbility to reduce.Therefore, poly-unit can only be made to operate under poor efficiency when producing high ethylene content impact polypropylene product; And when ensureing the normal production efficiency of poly-unit, but cannot improve the ethylene content of product, product grade is limited, greatly have impact on the economic benefit of enterprise.
Address this problem and usually adopt three kinds of methods: first method improves the thermal load of circulation gas interchanger, such as, use the interchanger with high heat load, or an interchanger of connecting after existing interchanger.But increase expense is invested by this scheme, and does not reduce the energy consumption level of device.Second method is improved the exchange capability of heat of circulation gas interchanger, method disclosed in Chinese patent CN1421468A, CN1887917A and CN1887918A, by strengthening the temperature difference between the cold and hot medium of circulation gas interchanger, and then effectively improve the heat exchange efficiency of interchanger.But the drawback of this method is, the active decay rapidly at higher than the temperature of 80 DEG C of conventional Zigler-Natta catalyzer, cause copolyreaction to be difficult to carry out, ethylene content and the rubber-phase content of product are difficult to the requirement that touches the mark.The third method extends the copolyreaction time, as mentioned the composition changing catalyst system in patent US0092656 and US5990251, and mention in patent US0152483 and CN1189505 and add accelerative activator in the copolyreaction stage, ensure that catalyzer still has sufficiently high polymerization activity in copolymerization stage.But this method can only improve the content of propylene-ethylene copolymers rubber phase component as a rule, due to the uncertainty on ethene and the impact of propylene monomer reactivity ratio, cause the ethylene content of the ethylene content in rubber phase or the finished product significantly not improve even to decline, affect shock resistance and the stress-whitening resistance energy of product.Therefore, need to find a kind of method improving ethene reactivity ratio, make the propylene-ethylene gas-phase copolymerization stage under lower vinyl monomer concentration, still can obtain having the impact polypropylene product of high ethylene content, do not increase the improvement cost of device simultaneously, reduce energy consumption, widen the ability of the process unit production premium quality product trade mark.
Summary of the invention
In order to overcome prior art when preparing high ethylene content impact polypropylene, copolymerization stage noncondensable gas concentration is high causes that circulation gas efficiency of heat exchanger is low, device capbility declines, energy consumption is high, plant modification high in cost of production defect, the object of this invention is to provide a kind of preparation method of impact polypropylene, make propylene and ethene under lower vinyl monomer concentration, be polymerized the impact polypropylene obtaining high ethylene content.This method avoid that noncondensable gas concentration is high causes that circulation gas efficiency of heat exchanger is low, device capbility declines, energy consumption is high, plant modification high in cost of production problem.
The invention provides a kind of preparation method of impact polypropylene, under ziegler natta catalyst and Nitrous Oxide exist, with propylene and ethene for raw material carries out polyreaction, described polyreaction is carried out in the polymerization reactor of at least two series connection.Particularly, said method comprising the steps of:
Step one, ziegler natta catalyst exist under carry out propylene homo reaction, obtain alfon;
Add the copolymerization that Nitrous Oxide carries out ethene and propylene under step 2, the existence of alfon that obtains in step one, obtain the impact polypropylene of high ethylene content;
Wherein, described step one is carried out under the reaction conditions of propylene gas phase-polymerization or liquid polymerization, and described step 2 is carried out under the reaction conditions of Ethylene-propylene Gas-phase Copolymerization.
In the present invention, the propylene homo reaction of step one is carried out in the first polymerization reactor, and does not have particular requirement to the form of polymerization reactor, gas phase or Liquid-phase reactor.Optional Liquid-phase reactor has annular-pipe reactor, vertical stirred tank reactor, and optional Gas-phase reactor has fluidized-bed reactor, horizontal type agitated bed reactor and vertical mixing bed bioreactor.
The ethylene-propylene copolymer reaction of step 2 is carried out in the second polymerization reactor.Described second polymerization reactor is Gas-phase reactor, is preferably horizontal retort Gas-phase reactor.In one particular embodiment of the present invention, described horizontal retort Gas-phase reactor is with horizontal type stir shaft, and mixing speed is 10-150 rev/min, and agitating vane selects T-shaped, rectangle, tiltedly oar, gate, wedge shape or its combination.Described horizontal retort Gas-phase reactor adopts quench liquid to remove heat, namely by the cooling/condensation of circulation gas, and sprays propylene liquid to bed, absorbs heat remove system response heat by propylene liquid gasification.Circulation gas cooling/the condensing equipment of the type reactor is very responsive to the concentration of noncondensable gas in gas composition, excessive concentration will cause equipment remove hot scarce capacity, operating load raise, energy consumption increase and production capacity under degradation problem.If ethene reactivity ratio can be improved and reduce noncondensable gas concentration, the running condition of the type reactor effectively can be improved.
In one particular embodiment of the present invention, by Nitrous Oxide and the inert component (as nitrogen, argon gas) not participating in polyreaction, or carry out (as ethene, propylene) with reactor feed gas and mix, added in polymerization reaction system by the feedstock pipeline of the second polymerization reactor or circulation gas pipeline.According to the present invention, the add-on of Nitrous Oxide can require to be controlled by gas meter and electronic regulated valve according to the ethylene content in product, and by the gas composition in on-line analysis testing tool (as gas-chromatography) Real-Time Monitoring second polymerization reactor.The concentration of described Nitrous Oxide in the second polymerization reactor is 0.01-10ppm, preferred 0.01-5ppm, most preferably 1-3ppm.
In step one, described propylene gas phase or liquid phase homopolymerization preferably carry out under the following conditions: temperature is 50-100 DEG C, are preferably 60-90 DEG C; Pressure is 1-6MPa, is preferably 2-5MPa; Polymerization time is 20-120 minute, is preferably 30-90 minute.
In step 2, described Ethylene-propylene Gas-phase Copolymerization reaction is preferably carried out under the following conditions: temperature is 50-90 DEG C, is preferably 60-80 DEG C; Pressure is 1-5MPa, is preferably 2-4MPa; Polymerization time is 20-120 minute, is preferably 30-90 minute.
In step one of the present invention and step 2, the pressure of appearance is gauge pressure.
In step one, as being not particularly limited, the additional proportion of described ziegler natta catalyst and propylene, and the mol ratio of hydrogen/propylene is this area routine selection, has no special requirements.Under liquid-phase polymerization condition, the feed ratio of hydrogen and propylene is 0-2000ppm; Under gas phase polymerization condition, in gas phase composition, the mol ratio of hydrogen/propylene is 0-0.03.
In step 2, as being not particularly limited, add-on, both additional proportions of described ethene and propylene, and in reaction gas phase, the mol ratio of hydrogen/propylene is this area routine selection.In preferred reaction gas phase, the mol ratio of hydrogen/propylene is 0-0.03.
In the method for the invention, metallocene (Ziegler-Natta) catalyzer of use, by open in a large number, preferably use the catalyzer with high stereoselective, can prepare the alfon that isotactic index is greater than 95%.Described Ziegler-Natta catalyst comprises:
1) ingredient of solid catalyst of titaniferous;
2) alkylaluminium cpd; And
3) optional external donor compound.
Wherein, the mol ratio of the ingredient of solid catalyst of described titaniferous, described alkylaluminium cpd and described external donor compound is 1: 5-500: 0-500, is preferably 1: 25-100: 25-100.
Component 1 in the catalyzer that the present invention uses) ingredient of solid catalyst of titaniferous is by the catalytic product of titanium compound, magnesium compound and internal electron donor compound.Specifically be documented in Chinese patent CN85100997, CN93102795.0, CN98126383.6, CN98111/80.5, CN98126385.2, CN99125566.6, CN9912556/.4, CN00109216.2, CN02100900.7, CN201210426370.2.Described catalyzer can directly use, and also can add after pre-complexing and/or prepolymerization.
Component 2 in the catalyzer that the present invention uses) general formula of alkylaluminium cpd is
AlR
16 nX
3-n(I)。
R in formula (VI)
16for hydrogen or carbonatoms are the alkyl of 1-20, X is halogen, and n is the number of 1 < n≤3; Specifically can be selected from least one in triethyl aluminum, tri-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-octylaluminium, triisobutyl aluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium, ethyl aluminum dichloride, preferred triethyl aluminum or triisobutyl aluminium.
Component 3 in the catalyzer that the present invention uses) external donor compound is the silicoorganic compound shown in general formula (II),
R′
pR"
qSi(OR"′)
4-p-q(II)
In formula (II), R ' and R " identical or different, be selected from halogen independently of one another, aryl that cycloalkyl that alkyl that hydrogen atom, carbonatoms are 1-20, carbonatoms are 3-20, carbonatoms are 6-20 and carbonatoms are one in the haloalkyl of 1-20; R " ' for carbonatoms is the alkyl of 1-20, carbonatoms is the cycloalkyl of 3-20, carbonatoms is 6-20 aryl and carbonatoms be the one in the haloalkyl of 1-20; P and q is respectively the integer of 0-3, and p+q < 4.
Described external electron donor can be trimethylmethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, isopropyl butyldimethoxysilane, di-t-butyl dimethoxysilane, tertbutyl methyl dimethoxysilane, t-butylethyl dimethoxysilane, tertiary butyl propyldimethoxy-silane, ter /-butylisopropyl dimethoxysilane, Cyclohexyl Methyl Dimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclopentyl-methyl dimethoxysilane, cyclopentyl ethyl dimethoxysilane, dicyclopentyl dimethoxyl silane, cyclopentyl cyclohexyl dimethoxysilane, two (2-methylcyclopentyl) dimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, propyl trimethoxy silicane, isopropyltri-methoxysilane, butyl trimethoxy silane, butyl triethoxyl silane, trimethoxysilane, amyltrimethoxysilane, isopentyl Trimethoxy silane, cyclopentyl-trimethoxy-silane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, n-propyl Trimethoxy silane, vinyltrimethoxy silane, tetramethoxy-silicane, tetraethoxysilane, one or more in four butoxy silanes, at least one in preferred dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, preferred diisopropyl dimethoxy silane further.
Present invention also offers the impact polypropylene of the high ethylene content prepared by aforesaid method, in described impact polypropylene) total ethylene content is 8-30wt%, rubber-phase content is 20-50wt%, preferred rubber mutually in ethylene content be 30-60wt%.
The Nitrous Oxide that the present invention adds in step 2 coordinates with ziegler natta catalyst, ethene reactivity ratio in the Propylene polymerization reaction of effective raising step 2, the vinyl monomer concentration in gas phase composition is reduced while ensureing product height ethylene content, reduce production energy consumption, what meet existing condensation/refrigerating unit removes heat energy power.
In addition, described Nitrous Oxide has oxidation capacity under the high temperature conditions, can by the Ti in ziegler natta catalyst
3+be oxidized to Ti
4+, make amount of activated center inactivation, oxygen, carbon monoxide, water etc. can be replaced to kill agent alive, control the reaction process in gas-phase copolymerization stage, prevent implode and sticky still phenomenon.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below will be described the present invention by embodiment.
In embodiment, polymkeric substance relevant data obtains by following testing method:
(1) ethylene content (RCC2) and rubber-phase content (RC) in total ethylene content (TOTC2), rubber phase: ThermoNicolet200 type infrared spectrum analyser is at 720-730cm
-1the corresponding total ethylene content TOTC2 of peak area at place; 730-740cm
-1the corresponding free state ethylene content of peak area at place, 720cm
-1, 727cm
-1, 729cm
-1the peak area corresponding copolymerization state ethylene content at place, the ratio of the ethylene content of free state and copolymerization state is ethylene content RCC2 in rubber phase.
Rubber-phase content (RC): according to formula
calculate.
(2) modulus in flexure: measure according to ASTMD790-97.
(3) tensile strength: measure according to ASTMD638-00.
(4) hit intensity in Izod: measure according to ASTMD256-00.
(5) 721 spectrophotometers of the titanium content in catalyzer are tested.
(6) grain size of alkoxyl magnesium and catalyzer, size-grade distribution MalvernMastersizerTM2000 laser diffractometry are measured, and normal hexane is dispersion agent (wherein, SPAN=(D90-D10)/D50).
(7) mensuration of the m value in carrier: get 0.1 gram of carrier, add 10mL1.2mol/L aqueous hydrochloric acid, shakes and makes it decompose in 24 hours, uses gas-chromatography quantitative, be then calculated as follows m value to ethanol wherein and 2-Ethylhexyl Alcohol:
In formula, w1 is 2-Ethylhexyl Alcohol quality, and w2 is ethanol quality.
(8) in olefin polymerization catalyst components, internal electron donor content uses Waters600E liquid chromatography to carry out measuring or gas Chromatographic Determination.
(9) quench liquid spray flux is the data that quench liquid nozzle flow meter reads from poly-unit.
Preparation example
This preparation example is used for the ingredient of solid catalyst of the titaniferous prepared in Ziegler-Natta catalyst.
After fully replacing the 16L voltage-resistant reactor with agitator with nitrogen, in reactor, add 10L ethanol, 300mL2-ethylhexanol, 11.2g iodine, 8g magnesium chloride and 640g magnesium powder.Stir and make system back flow reaction simultaneously, till no longer including hydrogen discharge.Stopped reaction, with 3L ethanol product washed, filter, dry, obtain alkoxyl magnesium carrier.Described alkoxyl magnesium carrier D50=30.2um, Span=0.81, m=0.015.Get above-mentioned alkoxyl magnesium carrier 650g and toluene 3250mL and be mixed with suspension.Repeating in the withstand voltage reactor of 16L of replacing through high pure nitrogen, add toluene 2600mL and titanium tetrachloride 3900mL, be warming up to 80 DEG C, then the suspension prepared is added in still, constant temperature 1 hour, adds diethyl phthalate 130mL, is slowly warming up to 110 DEG C, constant temperature 2 hours, press filtration obtains solid substance.The mixed solution that gained solid substance adds toluene 5070mL and titanium tetrachloride 3380mL 110 DEG C of stir process 1 hour, so process 3 times.The solid hexanes wash that repetition press filtration obtains 4 times, each 6000mL, press filtration, drying, obtain the ingredient of solid catalyst of titaniferous.Titanium atom content 2.4wt% in the ingredient of solid catalyst of gained titaniferous, diethyl phthalate content 10.5wt%.
Embodiment 1
The present embodiment is used for illustrating in the method for the high ethylene content impact polypropylene of preparation, and Nitrous Oxide can improve ethene reactivity ratio.
1) raw material
Adopt the ziegler natta catalyst obtained in preparation example as Primary Catalysts; Triethyl aluminum is promotor; Diisopropyl dimethoxy silane (DIPDMS) is external electron donor; Propylene, ethene and hydrogen are polymerization-grade, use after removing water, oxygen; Hexane uses after dehydration; Nitrous Oxide and nitrogen are made into mixed gas use according to the mol ratios of 1: 25.
2) testing apparatus
Adopt the polymerization technique of two horizontal retort Gas-phase reactor series connection.Horizontal retort Gas-phase reactor volume 0.2 cubic metre, stirring rake is T-shaped oblique blade, and angle of inclination is 10 degree, and stirring velocity is 100 revs/min.
3) process of the test
(1) step gas-phase propene homopolymerization: add Primary Catalysts, triethyl aluminum, external electron donor and propylene and carry out polyreaction in the first horizontal retort Gas-phase reactor.Wherein, the inlet amount of Primary Catalysts, triethyl aluminum, external electron donor is respectively 0.9g/hr, 0.072mol/hr, 0.012mol/hr, Al/Si (mol/mol)=8.59; Propylene feed amount is 15kg/hr; In reaction gas phase, hydrogen/propylene molar ratio is 0.033; The temperature of polyreaction is 85 DEG C, and pressure is 2.5MPa, and the time is 60 minutes, obtains propylene homo product;
(2) step propylene and ethene gas-phase copolymerization: in the second horizontal retort Gas-phase reactor, under the existence of the propylene homo product obtained in (1) step, added the mixed gas of Nitrous Oxide and nitrogen by feedstock pipeline, and unstripped gas ethene and propylene carry out polyreaction.Ethene and propylene feed amount are respectively 3.6kg/hr, 15kg/hr, and ethylene/propene mol ratio is 0.45; In reaction gas phase, hydrogen/propylene molar ratio is 0.039; The temperature of polyreaction is 66 DEG C, and pressure is 2.4MPa, and the time is 80 minutes, obtains final polymerisate, i.e. impact polypropylene product.Concrete technology condition is in table 1.
4) test-results
Carry out the long run test of 48 hours according to above-mentioned condition, device stable operation, the polymkeric substance be obtained by reacting has been carried out analytical test, the results are shown in table 1.
In embodiment 2 and embodiment 3, except (2) step propylene of process of the test is different with the add-on of Nitrous Oxide in ethene gas phase polymerization process, other condition is with embodiment 1, and concrete technology condition and test-results are in table 1.
Comparative example 1
When this comparative example is used for illustrating that in gas phase composition, vinyl monomer concentration is identical, do not add Nitrous Oxide, in impact polypropylene product, ethylene content will reduce.
Except not adding except Nitrous Oxide in (2) step propylene of process of the test and ethene gas phase polymerization process, other condition is with embodiment 1, and concrete technology condition and test-results are in table 1.
Comparative example 2
When this comparative example is used for illustrating the impact polypropylene product obtaining identical ethylene content, do not add Nitrous Oxide, the vinyl monomer concentration in gas phase composition will increase.
Do not add Nitrous Oxide except in (2) step propylene of process of the test and ethene gas phase polymerization process, improve ethylene, propylene as required than outward, other condition is with embodiment 1, and concrete technology condition and test-results are in table 1.
As can be seen from Table 1, the testing data of embodiment 1,2 and 3 mainly reflects the impact of Nitrous Oxide add-on on ethene reactivity ratio.When in second Gas-phase reactor, ethene is identical with propylene molar ratio, Nitrous Oxide is increased to 3ppm gradually by 1ppm, the ethylene content of its product, rubber-phase content, and the ethylene content in rubber phase also raises gradually thereupon, illustrate that Nitrous Oxide has obvious promoter action to raising ethene reactivity ratio.
The testing data of embodiment 1 and comparative example 1 mainly reflects the impact of Nitrous Oxide on ethene reactivity ratio.When in second Gas-phase reactor, ethene is identical with propylene molar ratio, embodiment 1 adds Nitrous Oxide, the ethylene content of its product, rubber-phase content, and the ethylene content in rubber phase is all higher than the comparative example 1 not adding Nitrous Oxide, illustrate that Nitrous Oxide has obvious promoter action to raising ethene reactivity ratio.Meanwhile, the product of embodiment 1 is when ethylene content improves, and tensile strength and modulus in flexure but obviously do not decline, and maintain good rigidity.
The testing data of embodiment 1 and comparative example 2 mainly reflects the impact of Nitrous Oxide on ethene reactivity ratio and plant energy consumption.When in the product of embodiment 1 and comparative example 2, ethylene content keeps suitable, the Nitrous Oxide that embodiment 1 adds improves ethene reactivity ratio, and the ethene in its gas phase composition and propylene molar ratio are reduced to 0.44, and comparative example 2 up to 0.61.The increase of vinyl monomer concentration in comparative example 2, certainly will make the condensation/cooling apparatus load of device increase, be embodied in the quench liquid flow of the second Gas-phase reactor of comparative example 2 apparently higher than embodiment 1.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a preparation method for impact polypropylene, comprising:
Step one, ziegler natta catalyst exist under carry out propylene homo reaction, obtain alfon;
Add the copolymerization that Nitrous Oxide carries out ethene and propylene under step 2, the existence of alfon that obtains in step one, obtain the impact polypropylene of high ethylene content.
2. method according to claim 1, is characterized in that, it carries out in the polymerization reactor of at least two series connection, carries out propylene homo reaction, carry out ethylene propylene copolymer reaction in the second polymerization reactor in the first polymerization reactor.
3. method according to claim 2, is characterized in that, described Nitrous Oxide with do not participate in the inert component of polyreaction, or to mix with reaction raw materials gas, added by the feedstock pipeline of the second polymerization reactor or circulation gas pipeline.
4. according to the method in claim 2 or 3, it is characterized in that, the concentration of described Nitrous Oxide in the second polymerization reactor is 0.01-10ppm, preferred 0.01-5ppm, most preferably 1-3ppm.
5. method according to claim 1, is characterized in that, described step one is carried out under the reaction conditions of propylene gas phase-polymerization or liquid polymerization, and described step 2 is carried out under the reaction conditions of Ethylene-propylene Gas-phase Copolymerization.
6. method according to claim 5, is characterized in that, in step one, the temperature of reaction of step one propylene gas phase or liquid polymerization is 50-100 DEG C, is preferably 60-90 DEG C; Pressure is 1-6MPa, is preferably 2-5MPa; Polymerization time is 20-120 minute, is preferably 30-90 minute.
7. method according to claim 5, is characterized in that, the temperature of reaction of step 2 Ethylene-propylene Gas-phase Copolymerization is 50-90 DEG C, is preferably 60-80 DEG C; Pressure is 1-5MPa, is preferably 2-4MPa; Polymerization time is 20-120 minute, is preferably 30-90 minute.
8. the method according to any one of claim 1 to 7, is characterized in that, the ziegler natta catalyst of use comprises:
1) ingredient of solid catalyst of titaniferous;
2) alkylaluminium cpd; And
3) optional external donor compound.
9. method according to claim 8, is characterized in that, the mol ratio of the ingredient of solid catalyst of described titaniferous, described alkylaluminium cpd and described external donor compound is 1: 5-500: 0-500, is preferably 1: 25-100: 25-100.
10. the impact polypropylene that method prepares according to claim 1-9 any one, wherein total ethylene content is 8-30wt%, and rubber-phase content is 20-50wt%, preferred rubber mutually in ethylene content be 30-60wt%.
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| CN110551242A (en) * | 2018-05-31 | 2019-12-10 | 中国石油天然气股份有限公司 | Impact-resistant co-polypropylene and preparation method thereof |
| CN111269491A (en) * | 2020-03-24 | 2020-06-12 | 浙江大学 | Olefin gas-phase polymerization method |
| CN111875726A (en) * | 2020-08-12 | 2020-11-03 | 上海赛科石油化工有限责任公司 | Polypropylene production operation control method |
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| US20060223958A1 (en) * | 2005-03-31 | 2006-10-05 | Fischbuch D B | Processes for producing high density polyethylene |
| 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 |
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| CN110551242A (en) * | 2018-05-31 | 2019-12-10 | 中国石油天然气股份有限公司 | Impact-resistant co-polypropylene and preparation method thereof |
| 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 |
| CN111269491A (en) * | 2020-03-24 | 2020-06-12 | 浙江大学 | Olefin gas-phase polymerization method |
| CN111269491B (en) * | 2020-03-24 | 2021-06-22 | 浙江大学 | Olefin gas-phase polymerization method |
| CN111875726A (en) * | 2020-08-12 | 2020-11-03 | 上海赛科石油化工有限责任公司 | Polypropylene production operation control 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 |
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