CN105622809B - A kind of preparation method of the impact polypropylene of low VOC content - Google Patents
A kind of preparation method of the impact polypropylene of low VOC content Download PDFInfo
- Publication number
- CN105622809B CN105622809B CN201410602824.6A CN201410602824A CN105622809B CN 105622809 B CN105622809 B CN 105622809B CN 201410602824 A CN201410602824 A CN 201410602824A CN 105622809 B CN105622809 B CN 105622809B
- Authority
- CN
- China
- Prior art keywords
- electron donor
- external electron
- propylene
- dimethoxysilane
- stage
- 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
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention provides a kind of preparation methods of low VOC content impact polypropylene, it include: the propylene homo stage, propylene homo reaction is carried out in the presence of the Ziegler-Natta catalyst and hydrogen comprising the first external electron donor, obtains the stream 1 comprising homopolymer polymer A and the catalyst；Propylene copolymerization stage carries out the copolyreaction of propylene and alpha-olefin in the presence of the stream 1 and the second external electron donor, obtains the polypropylene stream 2 comprising homopolymer polymer A and copolymerized polymer B；Wherein, first external electron donor is trialkoxy silane, and the second external electron donor is dialkoxy silicane.This method is not required to use special catalyst, and big change is not needed to existing process unit yet, it can production has Narrow Molecular Weight Distribution, the impact polypropylene product that Ultra-low molecular weight constituent content is low, smell is low, VOC content is low.
Description
Technical field
The present invention relates to a kind of polyacrylic preparation methods, and in particular to a kind of preparation of low VOC content impact polypropylene
Method.
Background technique
Polypropylene includes homopolypropylene, copolymer polypropylene, graft polypropylene and impact polypropylene, excellent combination property,
It is widely used in the fields such as automobile, household electrical appliance, building, amenities, chemical materials, package packing supplies.However polypropylene material
Different from metal material, there are the precipitation of small-molecular-weight volatile organic matter matter, i.e. VOC in synthesis, processing and use process
(volatile organic compounds) component is precipitated, and emits bad smell simultaneously, in spies such as enclosure space, food and medicine utensils
The use in different field is limited, and the especially occasions such as automotive interior material, household electrical appliance, the requirement to VOC content is higher and higher.Cause
This, needs to handle polypropylene material, reduces VOC content to meet the requirement to material.
Present industry is mainly controlled from raw material selection and processing technology stage.Acrylic resin mainly selects directly poly-
Legal production, without the sample using peroxide degradation, as patent document CN200910037827 is poly- using hydrogen-regulating method copolymerization
Propylene replaces the polypropylene of peroxide degradation to effectively reduce VOC content, but still compared with industry technology demand gap；EP
1988122A1 uses metallocene polypropylene resins to prepare the automotive interior material of low VOC for matrix resin, the disadvantage is that metallocene is urged
Agent, especially co-catalyst are at high cost, and compared with the product of traditional Ziegler-Natta catalyst, competitiveness is poor.
The method generallyd use now both at home and abroad is to handle in the process segment sample, to reduce VOC content.It is common
Method there are mainly three types of: physical method, chemical method and physical-chemical method.
Physical method is mainly the method that adsorbent absorbs with vacuumizes degassing in melting process.Such as patent document
CN201110165675 and CN200510026760 are reported using C25~45Fatty acid compound+Nano-class zinc oxide+receive
The adsorbent of meter level titanium oxide composition effectively reduces the VOC content of polypropylene material；CN200510028339 is used800~6000 mesh Kiselgel A of fineness reduces polypropylene VOC content；CN200710173555 uses quaternary
Surfactant-modified concave convex rod prepares adsorbent, effectively reduces the VOC content of polypropylene material；CN200910199792 is adopted
The VOC content of polypropylene material is reduced with BX molecular sieve and ZEOFLAIR mixed adsorbent；CN201010266765 uses hydrogen
Type high silica alumina ratio porous molecular screen reduces the VOC content of polypropene composition；CN201010529850 is using molecular sieve, boiling
The adsorbent of stone, hydroxyapatite and silicate mineral composition effectively reduces polyacrylic smell；CN201010543461 and
Patent application CN201210223887 is reported using the adsorbent being made of zinc ricinate+metal oxide+clay mineral
Reduce the smell of polypropylene material；CN201010590860 uses the adsorbent being made of clay, zeolite and metal oxide
The smell of polypropylene material is reduced, material has reached 3 grades of PV3900 standard；CN20111025209 and
CN201110443076 uses the white carbon black of 1000~5000 mesh to reduce the smell of polypropylene material for adsorbent；Patent application
CN201210230997 and patent application CN201210421186 adsorbs volatility object using liquid extractant such as alkoxy silane
Matter reduces polypropylene VOC content；Patent application CN201210550324 and patent application CN201310750693 uses epoxy
Ethane and propylene oxide block copolymer are that adsorbent reduces polypropylene VOC content；Patent application CN201310484744 is adopted
It is reduced with (9Z, 12R)-ricinoleic acid zinc salt/3,5- di-t-butyl -4- hydroxycinnamic acid composition eliminating smell agent
The VOC content of polypropylene material；CN201110083077 and patent application CN201210428771 passes through addition form of finely divided powder, mehtod
Silicon rubber reduces the VOC total amount of polypropylene material；US5109056 and patent application CN201110252124 is used and had been granulated
The method vacuumized in journey reduces VOC content.
Chemical method is mainly that chemical reaction occurs with volatile organic matter by the substance with active group to generate
The substance of not volatile, low smell is realized.As CN201110106732 using chelating type can response type organic salt (such as W1000,
F926) with the substance reaction that evaporates, to reduce VOC content；CN201210070870 uses benzofuranone type free
Base agent for capturing inhibits the VOC content of polypropylene material；US4851499 uses a kind of esterified glycerol ester type compound, Yi Zhonghuan
Oxygen class compound, a kind of alcohol compound, a kind of fatty acid ester compound or above-mentioned several compounds mixture, squeezing out
So that these compounds and the esters residue with peculiar smell is carried out ester exchange reaction in the process and form macromolecular compound, to drop
The low VOC content of polypropylene material；CN200910037827 is made using the nano-titanium dioxide of cerium particle doping in visible light
With lower decomposition small organic molecule, to achieve the purpose that reduce polypropylene material smell；US20100160710 is decomposed using mushroom
Volatile organic matter, to reduce the VOC content of polypropylene material.
Physical-chemical method is the method that physical absorption and chemical reaction combine, if CN201110241090 is by adding
Add a kind of plant fiber, by its hollow and porous structure feature and fiber itself with active group, pass through object
Reason absorption and chemical bonding collective effect, achieve the purpose that reduce polypropylene material VOC content.
Above method was completed in the process segment, no matter physical absorption or was chemically reacted, and it is poly- to play reduction
The effect of propylene VOC content, however not to Ultra-low molecular weight component or hydrocarbon compound existing for polypropylene matrix material
Fundamentally remove, and the root that these exactly cause sample smell, VOC content high.In addition, either adsorbent, chemistry
The use of reactant or vacuum plant will definitely increase cost.In addition, either physical method, chemical method or physical-chemical
Method has a respective limitation, and the substance of the method absorption of physical absorption is old in long-term heat ageing, light there is also in system
Under change effect, there is the risk discharged again；Chemical method specific aim is stronger, generally just for a factor, cannot solve simultaneously
The certainly sporadic problem that various factors generates；Physical-chemical method needs multiple additives to be used cooperatively, to the performance shadow of material
Sound is bigger.
Some patent literature reports are carried out using Ziegler-Natta catalyst using asymmetric external electron donor technology
The production of high-performance polypropylene.Use tetraethoxysilane (TEOS) for the first outer electron as WO2003059966 is reported
Body, diisopropyl dimethoxy silane (DIPDMS) is the second external electron donor, by controlling the density of hydrogen of two reactors,
It is prepared for high melting means polypropylene.CN102532381,CN102532380,US7772338,US20030149196,US6900281,
US6111039, WO9521203, patent application 201210084757 and patent application 201210084804 propose in the first stage
With the good external electron donor of a kind of hydrogen regulation performance (such as TEOS), second stage hydrogen tonality difference the second external electron donor (such as
Dicyclopentyl dimethoxyl silane, DCPMS), it is prepared for wide molecular weight distribution, high melt flow polypropylenes material.
CN102134290, CN102134291, CN102884093, CN102040696, patent application 201110153453, patent application
201110153451, patent application 201110153438 and patent application 201210422726 report first reactor selection etc.
Normality is high, hydrogen response difference silane such as dicyclopentyl dimethoxyl silane is the first external electron donor, in second reactor plus
Entering the good siloxanes of hydrogen response such as tetraethoxysilane is the second external electron donor, by two reactor hydrogen gas concentrations
Control, finally obtained wide molecular weight distribution, linear high melt strength, propylene.Patent application 201410289350 and patent
Application 201410287666 is reported using organic amine external electron donor and the wide vertical structure of silanes external electron donor compounding preparation
The preparation method of regularity, broad molecular weight distribution polypropylene.Use the technology of asymmetric external electron donor to prepare width above
For the purpose of the polypropylene of molecular weight distribution, the first external electron donor of use has wider molecular weight distribution, therefore, final poly-
The molecular weight distribution for closing object is wider, and Ultra-low molecular weight constituent content is high, sample VOC content is high.
Summary of the invention
The purpose of the present invention is to provide a kind of low smell of Narrow Molecular Weight Distribution, low VOC content impact polypropylene and
Preparation method.This method method different from the past that polypropylene material VOC content is reduced in post-processing, but from polypropylene
The mechanism of resin polymerization is set out, and fundamentally reduces Ultra-low molecular weight constituent content volatile in polymer, and then from root
The VOC content in material is reduced on source, thus provides a kind of extensive environment-friendly polypropylene material of applicability.
In the present invention, Ultra-low molecular weight component refers to weight average molecular weight Mw≤ 500 component.
According to the present invention, provide a kind of impact polypropylene, especially low VOC content impact polypropylene preparation side
Method, including with the next stage: the propylene homo stage, in the ziegler-nata (Ziegler-Natta) comprising the first external electron donor
Propylene homo reaction is carried out in the presence of catalyst and hydrogen, obtains the stream 1 comprising homopolymer polymer A and the catalyst；
Propylene copolymerization stage carries out the copolyreaction of propylene and alpha-olefin in the presence of the stream 1 and the second external electron donor, obtains
To the polypropylene stream 2 comprising homopolymer polymer A and copolymerized polymer B；Wherein, first external electron donor is tri-alkoxy
Silane, the second external electron donor are dialkoxy silicane.
In the present invention, so-called " low VOC content " refers to that the VOC constituent content in polypropylene is lower than 60 μ gC/g, especially
50 μ gC/g are less than, are tested according to the standard VDA278 of German automobiles industrial combination meeting.
In the logistics that the propylene homo stage obtains, the mixing comprising homopolymer polymer A and unreacted catalyst
Object.More specifically, unreacted catalyst is entrained in the homopolymer polymer A that reaction generates, so that the homopolymer polymer A
It shows with catalytic activity.It is this using homopolymer polymer A as carrier, using propylene homo stage unreacted catalyst as urging
The loaded catalyst form for changing active component, is advantageous the propylene copolyreaction of next step.
, according to the invention it is preferred to which the method also includes post-processing to polypropylene stream 2.The mode of post-processing can be with
It is and place to be dried it is known in the art, such as removing remaining catalyst, alkane and grease by conventional method
Reason, obtains polypropylene powder；Typical additives can also be further added, then extruding pelletization.
The Ziegler-Natta catalyst used in the method for the invention preferably has the catalyst of high stereoselective.
The Ziegler-Natta catalyst of high stereoselective described herein, which refers to, can be used for preparing isotactic index greater than 95%
Noblen catalyst.
The Ziegler-Natta catalyst being used in the present invention also includes the main catalyst component and organo-aluminium chemical combination of titaniferous
Object cocatalyst component；The main catalyst component also includes magnesium, halogen and internal electron donor；The internal electron donor can select
From at least one of two esters well known in the art, ethers, succinate compound, 1,3- alkoxide and sulfamide compound；
The organo-aluminum compound is preferably alkyl aluminum compound, more preferably trialkyl aluminium compound, such as: triethyl aluminum, three isobutyls
Base aluminium, three n-butylaluminums and three hexyl aluminium etc..
Wherein, available main catalyst component (and can be described as active solid catalyst component) can be in this field
Well-known to, this kind of specific example containing active solid catalyst component is for example disclosed in Chinese patent literature
CN85100997、CN98126383.6、CN98111780.5、CN98126385.2、CN93102795.0、CN00109216.2、
In CN99125566.6, CN99125567.4 and CN02100900.7, their full content is incorporated by reference into the present invention
In.
In the Ziegler-Natta catalyst being used in the present invention, the main catalyst component and organo-aluminum compound of titaniferous
Molar ratio in terms of aluminium/titanium be preferably 10:1~500:1, more preferably 40:1~150:1.
In the present invention, the preferred chemical general formula of the first external electron donor is R1Si(OR2)3Trialkoxy silane compound
At least one of；Wherein, R1Selected from C1-C20Straight chain, branching or cricoid aliphatic group, or it is selected from C1-C20It is nitrogenous
Heteroatomic straight chain, branching or cricoid organic group, R2For C1-C4Straight chain or branching aliphatic group.Also, R1
It is preferably selected from C1-C20Nitrogenous heteroatomic straight chain, branching or cricoid organic group for example, includes amino, amido, pyrrole
The organic group of the nitrogen-containing groups such as piperidinyl, pyrrole radicals or piperidyl.Trialkoxy silane chemical combination as the first external electron donor
The specific example of object includes but is not limited to isobutyl triethoxy silane, trimethoxysilane, isobutyl group tripropoxy
Silane, n-propyl triethoxysilane, isopro-pyltriethoxysilane, diethylamino triethoxysilane, 3- aminopropyl
Triethoxysilane, diethylin methyltriethoxysilane, dimethylamino methyl triethoxysilane, diisopropylamine ylmethyl
Triethoxysilane, di-n-propylamine ylmethyl triethoxysilane, 3- (2- aminoethylamino) propyl-triethoxysilicane, 3-
(2- aminoethylamino) propyl trimethoxy silicane, piperidyl triethoxysilane, pyrrole radicals triethoxysilane etc., preferably
For 3- aminocarbonyl propyl triethoxysilane, 3-aminopropyltriethoxysilane, diethylamino triethoxysilane, pyridyl group
At least one of triethoxysilane etc..
Preferably, the molar ratio of the organo-aluminum compound in catalyst and first external electron donor is calculated as with aluminium/silicon
1:1~60:1, preferably 5:1~30:1.
In the present invention, the preferred chemical general formula of the second external electron donor is R3R4Si(OR5)2Dialkoxy silicane chemical combination
At least one of object；Wherein, R3And R4It is each independently selected from C1-C12Straight chain, branching or cricoid aliphatic group or
C3-C12Nitrogenous cyclic organic group；R5For C1-C4Straight chain or branching aliphatic group.Two as the second external electron donor
The specific example of alkoxysilane compound containing trialkylsilyl group in molecular structure includes but is not limited to methyl-cyclopentyl-dimethoxysilane, methyl-isopropyl-two
Methoxy silane, isopropyl-cyclopenta-dimethoxysilane, bipyridyl dimethoxysilane, hydrogen isoquinoline dimethoxy of enjoying a double blessing
Base silane, ethyI-cyclopentyl-dimethoxysilane, n-propyl-cyclopenta-dimethoxysilane, isopropyl-cyclopenta-diformazan
Oxysilane, two (2- methyl butyl)-dimethoxysilanes, two (3- methyl butyl)-dimethoxysilanes, 2- methyl butyl-
3- methyl butyl-dimethoxysilane, two (2,2- Dimethyl-propyl)-dimethoxysilanes, 2- methyl butyl -2,2- diformazan
Base-propyl-dimethoxysilane, 3- methyl butyl -2,2- Dimethyl-propyl-dimethoxysilane, dimethyl-dimethoxy
Silane, dimethyl-diethoxy silane, diisopropyl-dimethoxysilane, diisopropyl-diethoxy silane, two isobutyls
Base-dimethoxysilane, diisobutyl-diethoxy silane, methyl-cyclohexyl base-dimethoxy silane, methyl-isobutyl-diformazan
Oxysilane, dicyclohexyl-dimethoxysilane, dicyclohexyl-diethoxy silane, bicyclopentyl-dimethoxysilane, two
Cyclopenta-diethoxy silane etc..
Preferably, the molar ratio of the organo-aluminum compound in catalyst and second external electron donor is calculated as with aluminium/silicon
1:1~60:1, preferably 1:1~10:1.
In some embodiments of the present invention, the molar ratio of the second external electron donor and the first external electron donor is 1-
30, preferably 5-20.
Preferably, the molar ratio of the organo-aluminum compound in catalyst and first external electron donor is calculated as with aluminium/silicon
1:1~60:1, preferably 5:1~30:1；Also, the molar ratio of the organo-aluminum compound and second external electron donor with
Aluminium/silicon is calculated as 1:1~60:1, preferably 1:1~10:1.
As described in the above content, the present inventor passes through many years in this field the study found that using a kind of special
External electron donor combination, be applied in propylene polymerization technique, can prepare narrow molecular weight distribution, low VOC content,
The impact polypropylene material of low smell.This combination is, good first with a kind of hydrogen response, can produce fluidity of molten
The catalyst that the first low external electron donor of height, narrow molecular weight distribution, Ultra-low molecular weight constituent content polymerize as propylene homo
Component, to prepare the continuous phase of impact polypropylene；Then good using a kind of copolymerization performance, high toughening effect rubber phase can be produced
Second external electron donor prepares the dispersed phase of impact polypropylene.The present inventor is further it has surprisingly been found that using as above
The trialkoxy silane and dialkoxy silicane can be real respectively as the first external electron donor and the second external electron donor
The existing effect has better effect especially in above-mentioned amount ranges.Since the VOC component in impact polypropylene mostlys come from
The homopolymerization of first stage, therefore a particularly pertinent advantage of the invention is, in the propylene homo stage advantageously with institute
Trialkoxy silane is stated as the first external electron donor, reduces the content of the Ultra-low molecular weight component in homopolymer polymer, and
With narrow molecular weight distribution, and then obtain the impact polypropylene material of low VOC value.Therefore, by the present invention in that with specific
External electron donor it is appropriately combined, realize the regulation of homopolymerization and copolymerization stage different catalysts property, and then prepare ultralow point
The impact polypropylene of low, the strong and unyielding good combination property of son amount constituent content, the outstanding feature with low VOC content, low smell.
In the method for the invention, in the propylene homo stage, the concentration of hydrogen is preferably 1000-20000ppm, further preferably
For 2000-10000ppm.
The hydrogen usage in the propylene homo stage, or not hydrogenation are used below in propylene copolymerization stage.
According to the method for the present invention, the productivity ratio of propylene homo stage and copolymerization stage is generally 40:60~60:40.
In the method for the invention, in the product homopolymer polymer A in propylene homo stage, Ultra-low molecular weight component, i.e.
Mw≤ 500 constituent content is very low, is less than or equal to 40ppm, for example, 0.5-40ppm.Due in impact polypropylene material
VOC component mostlys come from the homopolymerization stage of propylene, so ultralow in the product homopolymer polymer A in control propylene homo stage
Molecular weight component content has a very important significance the control of the VOC content of impact polypropylene product.When homopolymerization polymerize
When Ultra-low molecular weight constituent content in object A is very low, the VOC content of finally obtained impact polypropylene product then corresponding low, gas
Taste is also low.It is good using hydrogen response as described above in the homopolymerization stage that the present invention is exactly based on, and can produce Ultra-low molecular weight
The low trialkoxy silane of constituent content reduces the Ultra-low molecular weight of propylene homo stage product as the first external electron donor
Constituent content, to prepare the impact polypropylene material of low VOC content.
On the other hand, in the propylene homo stage of the method for the present invention, the molecular weight distribution of the homopolymer polymer A of generation is very
Narrow, i.e. Mw/MnLess than or equal to 5.0, generally higher than 2.0.This can produce three alkane of narrow molecular weight distribution again by using
Oxysilane reduces the molecular weight distribution of propylene homo stage product as the first external electron donor, and then prepares molecular weight point
Cloth is narrow, low VOC content impact polypropylene material.
Further, the melt mass flow rate (MFR) of homopolymer polymer A is greater than or equal to 50g/10min, such as
50-200g/10min.Herein, MFR is measured under 230 DEG C, 2.16kg load according to ASTM D1238.
In method provided by the invention, in the propylene homo stage, optionally include in propylene homo reaction raw materials
A small amount of alpha-olefin, such as contain the α-based on propylene and 0-10 weight %, the preferably 0-5 weight % of the total weight of alpha-olefin
Alkene.A small amount of comonomer is added in the propylene homo stage and carries out random copolymerization, the rigidity of adjustable final polymer refers to
Mark.Since the alpha-olefin being added is a small amount of, it will therefore be appreciated that although a small amount of propylene and α-alkene also have occurred at this stage
The copolyreaction of hydrocarbon, but key reaction is still the homopolymerization of propylene.
In the present invention, used alpha-olefin can be common alpha-olefin in propylene copolymerization, such as can be selected from second
At least one of alkene, 1- butylene, 1- hexene and 1- octene.
In the method for the invention, the catalyst comprising the first external electron donor can be added directly into homopolymerization device
In, it by the known pre- complexing of industry and/or prepolymerization and then can also be added in homopolymerization device.Pre- complexing is to urge
Cocatalyst component, external electron donor and main catalyst component (solid active center component) carry out caltalyst in agent system
The complex reaction of system.The form for the reactor being complexed in advance can be multiplicity, and the purpose is to keep catalyst components mixing equal
It is even, to obtain the catalyst system with polymerization activity, can be continuous stirred tank reactor, annular-pipe reactor, even can be with
It is a Duan Guanlu.Pre- 0~30min of complexation time, -10~20 DEG C of pre- complexation temperature.
Prepolymerization step is also optionally set after pre- complexing.The prepolymerization refers to catalyst in lower temperature
The lower prepolymerization for carrying out certain multiplying power, to obtain ideal particle shape and dynamic behavior control.The prepolymerization can be
The continuous prepolymerization of liquid-phase bulk, can also be batch pre-polymerization in the presence of an inert solvent.Prepolymerization temperature be usually -10~
50 DEG C, preferably 5~20 DEG C.
In a preferred embodiment of the invention, before copolyreaction, by the stream 1 and the described second outer electron
Body is pre-mixed, so that complexing occurs for the Ziegler-Natta catalyst in the stream 1 and second external electron donor instead
It answers.In a preferred embodiment, pre- complexation temperature is -10~20 DEG C, and pre- complexation time is 0~30min.It is anti-by the complexing
It answers, Ziegler-Natta catalyst used in homopolymerization polymerization reaction and the second external electron donor form in new catalytic activity
The heart changes the property of raw catalyst, is conducive to produce the rubber phase of high toughening effect in copolymerization stage.
There is provided according to the present invention impact polypropylene polymerization preparation method, can be and be carried out continuously, can also interval into
Row.Continuous polymerization can be two or more concatenated Liquid-phase reactor or gas-phase reactor, Liquid-phase reactor can be endless tube
Reactor or continuous stirred tank reactor, gas-phase reactor can be horizontal type agitated bed reactor or vertical mixing bed reactor
Or fluidized-bed reactor etc., the above Liquid-phase reactor and gas-phase reactor can also arbitrarily matched combineds.The present invention is with double
For endless tube+gas-phase apparatus (Spheripol technique), but it is not limited only to the technique.
In one embodiment of the invention, propylene homo stage and propylene copolymerization stage are in two or more strings
Be carried out continuously in the reactor of connection, and second external electron donor enter propylene copolymerization stage reactor before or
It is mixed in the feed end (or feed inlet) of the reactor of propylene copolymerization stage with the stream 1, so that neat in the stream 1
Complex reaction occurs for Ge Le-Natta catalyst and second external electron donor.
In a preferred embodiment of the invention, in the propylene homo stage, before homopolymerization, by the neat lattice
Le-Natta catalyst is complexed in advance and/or prepolymerization；Before copolyreaction, electricity will be given outside the stream 1 and described second
Daughter is pre-mixed, so that the Ziegler-Natta catalyst in the stream 1 is complexed with second external electron donor
Reaction.
The method provided according to the present invention, propylene homo stage can in the liquid phase, or carry out in the gas phase, or use
Liquid-gas combination technique carries out.When carrying out liquid phase polymerization, polymerization temperature can be 50~120 DEG C, preferably 60~90 DEG C；It is poly-
Resultant pressure should be higher than that saturated vapour pressure of the propylene under corresponding polymerization temperature.In gas-phase polymerization polymerization temperature can for 50~
120 DEG C, preferably 60~100 DEG C；Polymerization pressure can be normal pressure or higher, preferably pressure be 1.0~5.0MPa (gauge pressure, under
Together).The copolyreaction stage usually carries out in the gas phase, and polymerization temperature is 55~100 DEG C, preferably 60~90 DEG C；Polymerization pressure
It can be normal pressure or higher, preferably pressure is 1.0~3.0MPa.
The present invention also provides a kind of impact polypropylene being prepared by the above method, the impact polypropylene
VOC content according to German automobiles industrial combination can standard VDA278 test for less than or equal to 50 μ gC/g, such as
0.001-50μg·C/g.Further, the MFR of the impact polypropylene is greater than or equal to 20g/10min, such as 20-100g/
10min。
The preparation method of impact polypropylene provided by the invention, by first use it is good comprising hydrogen response, can produce point
The catalyst of first external electron donor of the homopolymer of son amount narrowly distributing be catalyzed under certain density of hydrogen propylene or propylene and
The polymerization of a small amount of alpha-olefin, obtains the homopolymer polymer A as continuous phase；Then the second external electron donor and homopolymerization products are added
Logistics is complexed in advance, generates new catalytic active center, is continued initiation propylene and is reacted with the conjunction of other alpha-olefin copolymers, is made
It is final that the impact polypropylene comprising continuous phase (polymer A) and rubber phase (polymer B) is made for the polymer B of rubber phase.It can
See, this method only passes through specific first external electron donor of selection and the second external electron donor is respectively used to accomplished continuously or intermittently operate
Propylene homopolymerization and copolymerization stage, and the dosage of external electron donor and the additional amount of hydrogen are adjusted, without being urged with special
Agent does not need big change to existing process unit yet, it can production has narrow molecular weight distribution, Ultra-low molecular weight group
Divide the impact polypropylene product that content is low, smell is low, VOC content is low.The experiment proved that the VOC of impact polypropylene of the invention
Lower than 50 μ gC/g.
It is comprehensive as it can be seen that low VOC impact polypropylene polymerization process operating procedure of the invention is simple and reliable, input cost compared with
It is low, well solve the deficiencies in the prior art.
Specific embodiment
The present invention is explained in further detail below in conjunction with specific embodiments, but the scope of the present invention is not
It is limited to these embodiments.
The related data of polymer are obtained by following test method in embodiment:
1. polymer room temperature xylene soluble content (being considered as rubber-phase content): being surveyed according to ASTM D5492 the method
It is fixed；
2. gaseous volatile organic matter VOC: being tested according to the standard VDA278 of German automobiles industrial combination meeting；
3. melt mass flow rate (MFR): according to GB/T 3682-2000 the method, with 7026 type of CEAST company
Fusion index instrument measures under 230 DEG C, 2.16kg load；
4. bending modulus: being measured according to GB/T 9341-2008 the method；
5. Izod impact strength: being measured according to GB/T 1843-2008 the method；
6. ethylene contents: being measured using infrared spectroscopy (IR) method；
7. molecular weight and its molecular weight distribution (Mw/Mn): PL-GPC is produced using Britain Polymer Laboratories company
The molecular weight for the IR4 detector combination measurement sample that 220 gel permeation chromatographs and Polymer Char company, Spain produce and
Molecular weight distribution, chromatographic column are 3 series connection 10 μm of MIXED-B columns of Plgel, and solvent and mobile phase are that 1,2,4- trichloro-benzenes (contain
0.3g/1000ml antioxidant 2,6- dibutyl p-cresol), 150 DEG C of column temperature, flow velocity 0.95mL/min.
Embodiment 1
Propylene polymerization carries out on a set of 25Kg/hr propylene polymerization device, and the device mainly includes pre- complex reactions
Device, pre-polymerization reactor, the first annular-pipe reactor, the second annular-pipe reactor and third gas-phase reactor.
Polymerization and steps are as follows:
(1) pre- complex reaction
Major catalyst (DQC-602 catalyst, Beijing Ao Da branch company, middle Effect of Catalysis In Petrochemistry agent company provide, Ti content:
2.4wt%, Mg content: 18.0wt%, n-butyl phthalate content: 13.0wt%) flow be 0.8g/hr, co-catalysis
Agent (triethyl aluminum, TEA) flow is 6.33g/hr, the first external electron donor (3- aminocarbonyl propyl triethoxysilane, KHTES) stream
Amount is 0.60g/hr, and TEA/KHTES ratio is 50 (mol/mol), the pre- complex reaction 8min at 6 DEG C.
(2) prepolymerization
Catalyst system after pre- complexing is added continuously and continuously stirs autoclave pre-polymerization reactor, in propylene liquid phase sheet
Prepolymerization is carried out under body environment, temperature is 15 DEG C, and the residence time is about 4min, and the pre-polymerization multiple of catalyst is under this condition
About 60~120 times.
(3) first stage propylene homo closes reaction
Catalyst after prepolymerization is continuously passed through in the first annular-pipe reactor and concatenated second annular-pipe reactor
It completes first stage propylene homo and closes reaction, two 70 DEG C of loop po lymerisation reaction temperature, reaction pressure 4.0MPa, two endless tubes are anti-
It answers and hydrogen is added in the charging of device, the density of hydrogen about 2800ppm of on-line chromatograph detection obtains homopolypropylene A.
(4) second stage copolymerization of propylene reacts
The dicyclopentyl dimethoxyl silane (DCPMS) of 1.2g/hr, TEA/ is added in the exit of the second annular-pipe reactor
DCPMS ratio is 5 (mol/mol), and wherein DCPMS is the second external electron donor, and DCPMS is before entering third gas-phase reactor
Be pre-mixed with the effluent of the second annular-pipe reactor, the material after mixing enters third reactor, herein carry out ethylene/
Copolymerization of propylene reacts, wherein ethylene/(ethylene+propylene)=0.40 (v/v).Also, it is added in third reactor a certain amount of
Hydrogen makes H2/ ethylene=0.06 (v/v), the density of hydrogen of on-line chromatograph detection are 2200ppm.It is obtained in third reactor
Ethylene/propylene copolymer closes reaction product ethylene-propylene copolymer B.
The final product C (polymer A and B) obtained after second stage is reacted is through in wet nitrogen removal unreacted device
The activity of catalyst, steam remove alkane and grease remaining in polymer, and heat drying obtains polymer powders.To polymerization
Added in obtained powder 168 additive of IRGAFOS of 0.1wt%, 0.2wt% 1010 additive of IRGANOX and
The calcium stearate of 0.05wt%, is granulated with double screw extruder.
The specific process parameter of the present embodiment, the performance test results of resulting polymers are listed in Tables 1 and 2.
Embodiment 2
Catalyst used in embodiment 2, pre- complexing and polymerization process condition are same as Example 1.It is different from embodiment 1
Place is: the first external electron donor KHTES additional amount increases, and TEA/KHTES is changed to 40 (mol/mol).The tool of the present embodiment
Body technology parameter, the performance test results of resulting polymers are listed in Tables 1 and 2.
Embodiment 3
Catalyst used in embodiment 3, pre- complexing and polymerization process condition are same as Example 1.It is different from embodiment 1
Place is: the first external electron donor KHTES being changed to diethylamino triethoxysilane (BEATES), TEA/BEATES changes
For 30 (mol/mol).The specific process parameter of the present embodiment, the performance test results of resulting polymers are listed in Tables 1 and 2.
Embodiment 4
Catalyst used in embodiment 4, pre- complexing and polymerization process condition are same as Example 1.It is different from embodiment 1
Place is: the first external electron donor KHTES being changed to 3-aminopropyltriethoxysilane (APTES), TEA/APTES adds
It is constant to enter amount, hydrogen is changed to 2500ppm in third reactor.The specific process parameter, the performance of resulting polymers of the present embodiment
Test result is listed in Tables 1 and 2.
Embodiment 5
Catalyst used in embodiment 5, pre- complexing and polymerization process condition are same as Example 1.It is different from embodiment 1
Place is: the first external electron donor KHTES being changed to pyridyl group triethoxysilane (PETES), TEA/PETES additional amount is not
Become, the density of hydrogen that the detection of hydrogen on-line chromatograph is added in the charging of annular-pipe reactor is changed to 4000ppm, hydrogen in third reactor
Gas is changed to 3000ppm.The specific process parameter of the present embodiment, the performance test results of resulting polymers are listed in Tables 1 and 2.
Embodiment 6
Catalyst used in embodiment 6, pre- complexing and polymerization process condition are same as Example 1.It is different from embodiment 1
Place is: the first external electron donor KHTES is changed to isobutyl triethoxy silane (IBTES), TEA/IBTES additional amount
(i.e. the additional amount of the first external electron donor) is constant.The performance test knot of the specific process parameter of the present embodiment, resulting polymers
Fruit is listed in Tables 1 and 2.
Embodiment 7
Catalyst used in embodiment 7, pre- complexing and polymerization process condition are same as Example 1.It is different from embodiment 1
Place is: the second external electron donor DCPMS being changed to isopropyl dicyclopentyldimetoxy silane (IPPMS), and changes its stream
Amount, makes TEA/IPPMS additional amount be adjusted to 10 (mol/mol).The specific process parameter, the performance of resulting polymers of the present embodiment are surveyed
Test result is listed in Tables 1 and 2.
Embodiment 8
Catalyst used in embodiment 8, pre- complexing and polymerization process condition are same as Example 1.It is different from embodiment 1
Place is: the density of hydrogen that the detection of hydrogen on-line chromatograph is added in the charging of annular-pipe reactor is changed to 5500ppm, third reaction
Hydrogen is changed to 3500ppm in device.The specific process parameter of the present embodiment, the performance test results of resulting polymers are listed in 1 and of table
In table 2.
Embodiment 9
Catalyst used in embodiment 9, pre- complexing and polymerization process condition are same as Example 1.It is different from embodiment 1
Place is: the density of hydrogen that the detection of hydrogen on-line chromatograph is added in the charging of annular-pipe reactor is changed to 9000ppm, third reaction
Hydrogen is changed to 4000ppm in device.The specific process parameter of the present embodiment, the performance test results of resulting polymers are listed in 1 and of table
In table 2.
Comparative example 1
Catalyst used in comparative example 1, pre- complexing and polymerization process condition are same as Example 1.It is different from embodiment 1
Place is: no longer separately adding the second external electron donor, continues the effect for playing the first external electron donor.That is the second external electron donor
It is identical with the first external electron donor, it is KHTES, additional amount is constant.The specific process parameter of the present embodiment, resulting polymers
The performance test results are listed in Tables 1 and 2.
Comparative example 2
Catalyst used in comparative example 2, pre- complexing and polymerization process condition are same as Example 1.It is different from embodiment 1
Place is: closing the first external electron donor of reaction using DCPMS as first stage propylene homo, and no longer separately plus outside second gives
Electron continues the effect for playing the first external electron donor.I.e. the second external electron donor is identical as the first external electron donor, is
DCPMS, additional amount are constant.The specific process parameter of the present embodiment, the performance test results of resulting polymers are listed in Tables 1 and 2
In.
Comparative example 3
Catalyst used in comparative example 3, pre- complexing and polymerization process condition are same as Example 1.It is different from embodiment 1
Place is: the first external electron donor uses DCPMS, and the second external electron donor uses KHTES, and additional amount is constant.The present embodiment
Specific process parameter, the performance test results of resulting polymers are listed in Tables 1 and 2.
As can be seen from Table 2, the present invention uses first external electron donor of a certain amount of trialkoxy silane as catalyst,
In the presence of a certain amount of hydrogen carry out propylene homo reaction, and using a certain amount of dialkoxy silicane as catalyst second
External electron donor is catalyzed propylene copolyreaction, obtains that molecular weight distribution is relatively narrow, impact polypropylene of low VOC content.Also,
In a certain range, the additional amount of the first external electron donor is bigger, and the polymer molecular weight dispersion of distribution is narrower, and VOC content is lower.
Although the present invention has been described in detail, it will be understood by those skilled in the art that in spirit and scope of the invention
Modification will be apparent.However, it should be understood that various aspects, the different specific embodiments that the present invention records are (square
Case) each section and the various features enumerated can be combined or all or part of exchange.In above-mentioned each specific embodiment
In, those can suitably be combined with other embodiment with reference to the embodiment of another embodiment, this is will be by this
Field technical staff is to understand.In addition, it will be understood to those of skill in the art that the description of front is only exemplary mode,
It is not intended to limit the present invention.
Claims (15)
1. a kind of preparation method of low VOC content impact polypropylene, including with the next stage:
The propylene homo stage: third is carried out in the presence of the Ziegler-Natta catalyst and hydrogen comprising the first external electron donor
Polyamino alkenyl reaction, obtains the stream 1 comprising homopolymer polymer A and catalyst；
Propylene copolymerization stage: carrying out propylene in the presence of the stream 1 and the second external electron donor and the copolymerization of alpha-olefin is anti-
It answers, obtains the polypropylene stream 2 comprising homopolymer polymer A and copolymerized polymer B；
Wherein, first external electron donor is diethylamino triethoxysilane, and the second external electron donor is dialkoxy
The molar ratio of silane, second external electron donor and first external electron donor is 5-20；
The Ziegler-Natta catalyst also includes the main catalyst component and organo-aluminum compound cocatalyst component of titaniferous；
The molar ratio of the organo-aluminum compound and first external electron donor is 30；Institute is used below in the propylene copolymerization stage
The hydrogen usage in propylene homo stage is stated, or not hydrogenation.
2. the method according to claim 1, wherein second external electron donor is selected from chemical general formula
R3R4Si(OR5)2At least one of dialkoxysilane compounds；Wherein, R3And R4It is each independently selected from C1-C12Straight chain
, branching or cricoid aliphatic group or C3-C12Nitrogenous cyclic organic group；R5For C1-C4Straight chain or branching aliphatic series
Group.
3. method according to claim 1 or 2, which is characterized in that the main catalyst component also includes magnesium, halogen and interior
Electron donor；The internal electron donor is selected from two esters, ethers, succinate compound, 1,3- alkoxide and sulfamide compound
At least one of；The organo-aluminum compound is alkyl aluminum compound.
4. according to the method described in claim 3, it is characterized in that, the organo-aluminum compound and second external electron donor
Molar ratio 1:1~60:1 is calculated as with aluminium/silicon.
5. according to the method described in claim 4, it is characterized in that, the organo-aluminum compound and second external electron donor
Molar ratio 1:1~10:1 is calculated as with aluminium/silicon.
6. method according to claim 1 or 2, which is characterized in that in the propylene homo stage, the concentration of hydrogen is
1000-20000ppm。
7. according to the method described in claim 6, it is characterized in that, the concentration of hydrogen is excellent to be in the propylene homo stage
2000-10000ppm。
8. method according to claim 1 or 2, which is characterized in that in the homopolymer polymer A, Mw≤ 500 component
Weight content is 0.5~40ppm；And/or Mw/MnLess than or equal to 5.0, it is greater than 2.0.
9. method according to claim 1 or 2, which is characterized in that the alpha-olefin is selected from ethylene, 1- butylene, 1- hexene
At least one of with 1- octene；It optionally include 0~10 in propylene homo reaction raw materials and in the propylene homo stage
The alpha-olefin of weight %, the total weight based on propylene and alpha-olefin.
10. method according to claim 1 or 2, which is characterized in that in the propylene homo stage, homopolymerization it
Before, the Ziegler-Natta catalyst is complexed and/or prepolymerization in advance；Before copolyreaction, by the stream 1 with
Second external electron donor is pre-mixed, so as to give outside the Ziegler-Natta catalyst in the stream 1 and described second
Complex reaction occurs for electron.
11. according to the method described in claim 10, it is characterized in that, the propylene homo stage and propylene copolymerization stage are two
It is carried out continuously in a or more than two concatenated reactors, and second external electron donor is entering propylene copolymerization stage
The feed end of reactor before reactor or in propylene copolymerization stage is mixed with the stream 1.
12. method according to claim 1 or 2, which is characterized in that second external electron donor is selected from methyl-ring penta
Base-dimethoxysilane, methyl-isopropyl-dimethoxysilane, isopropyl-cyclopenta-dimethoxysilane, bipyridyl
Dimethoxysilane, hydrogen isoquinoline dimethoxysilane of enjoying a double blessing, ethyI-cyclopentyl-dimethoxysilane, n-propyl-cyclopenta-
Dimethoxysilane, isopropyl-cyclopenta-dimethoxysilane, two (2- methyl butyl)-dimethoxysilanes, two (3- methyl
Butyl)-dimethoxysilane, 2- methyl butyl -3- methyl butyl-dimethoxysilane, two (2,2- Dimethyl-propyls)-two
Methoxy silane, 2- methyl butyl -2,2- Dimethyl-propyl-dimethoxysilane, 3- methyl butyl -2,2- dimethyl-the third
Base-dimethoxysilane, dimethyl-dimethoxysilane, dimethyl-diethoxy silane, diisopropyl-dimethoxy silicon
Alkane, diisopropyl-diethoxy silane, diisobutyl-dimethoxysilane, diisobutyl-diethoxy silane, methyl-ring
Hexyl-dimethoxy silane, methyl-isobutyl-dimethoxysilane, dicyclohexyl-dimethoxysilane, dicyclohexyl-diethyl
At least one of oxysilane, bicyclopentyl-dimethoxysilane, bicyclopentyl-diethoxy silane.
13. method according to claim 1 or 2, which is characterized in that the reaction temperature in the propylene homo stage be 50~
120℃；The reaction temperature of the propylene copolymerization stage is 55~100 DEG C.
14. according to the method for claim 13, which is characterized in that the reaction temperature in the propylene homo stage is 60~95
℃；The reaction temperature of the propylene copolymerization stage is 60~90 DEG C.
15. the impact polypropylene that method described in any one of -14 is prepared according to claim 1, the anti-impact poly- third
The VOC content of alkene is according to the standard VDA278 test of German automobiles industrial combination meeting for less than 50 μ gC/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410602824.6A CN105622809B (en) | 2014-10-31 | 2014-10-31 | A kind of preparation method of the impact polypropylene of low VOC content |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410602824.6A CN105622809B (en) | 2014-10-31 | 2014-10-31 | A kind of preparation method of the impact polypropylene of low VOC content |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105622809A CN105622809A (en) | 2016-06-01 |
| CN105622809B true CN105622809B (en) | 2019-03-22 |
Family
ID=56038186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410602824.6A Active CN105622809B (en) | 2014-10-31 | 2014-10-31 | A kind of preparation method of the impact polypropylene of low VOC content |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105622809B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022221049A1 (en) * | 2021-04-15 | 2022-10-20 | Exxonmobil Chemical Patents Inc. | Processes for making improved polypropylene homopolymers, random copolymers, and impact copolymers |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102632778B1 (en) * | 2016-08-30 | 2024-02-02 | 더블유.알. 그레이스 앤드 컴파니 -씨오엔엔. | Catalyst systems for polyolefin production and methods of making and using the same |
| BR112019022774B1 (en) * | 2017-05-30 | 2023-03-07 | Basell Poliolefine Italia S.R.L | COMPOSITION OF POLYPROPYLENE AND AUTOMOTIVE INTERNAL ELEMENT COMPRISING IT |
| JP7361680B2 (en) * | 2018-04-20 | 2023-10-16 | 東邦チタニウム株式会社 | Method for producing olefin polymers |
| CN111100225B (en) * | 2018-10-29 | 2022-08-19 | 中国石油化工股份有限公司 | Propylene polymerization method and device |
| WO2022015627A2 (en) | 2020-07-17 | 2022-01-20 | Exxonmobil Chemical Patents Inc. | Polymers with low levels of volatile organic compounds and methods of making such polymers |
| CN114437264B (en) * | 2020-10-20 | 2024-03-26 | 中国石油化工股份有限公司 | Low-VOC low-odor polypropylene resin and preparation method and application thereof |
| CN115521544B (en) * | 2022-10-21 | 2024-08-20 | 中国石油化工股份有限公司 | Low-VOC (volatile organic compound) high-fluidity high-impact polypropylene material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532381A (en) * | 2010-12-24 | 2012-07-04 | 中国石油化工股份有限公司 | Polymerization method of anti-impact propylene copolymer having high melt flowability |
| CN102816270A (en) * | 2011-06-09 | 2012-12-12 | 中国石油化工股份有限公司 | High-melt-strength propylene/butene copolymer and preparation method thereof |
| CN102816269A (en) * | 2011-06-09 | 2012-12-12 | 中国石油化工股份有限公司 | High-melt-strength propylene/ethylene copolymer and preparation method thereof |
| CN102816271A (en) * | 2011-06-09 | 2012-12-12 | 中国石油化工股份有限公司 | High-melt-strength propylene/ethylene/butene copolymer and preparation method thereof |
| CN103571044A (en) * | 2012-08-03 | 2014-02-12 | 中国石油化工股份有限公司 | Preparation method of high-impact-strength polypropylene kettle internal alloy |
| CN103788256A (en) * | 2012-10-30 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of high-melt fluidity high-rigidity antishock polypropylene |
-
2014
- 2014-10-31 CN CN201410602824.6A patent/CN105622809B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532381A (en) * | 2010-12-24 | 2012-07-04 | 中国石油化工股份有限公司 | Polymerization method of anti-impact propylene copolymer having high melt flowability |
| CN102816270A (en) * | 2011-06-09 | 2012-12-12 | 中国石油化工股份有限公司 | High-melt-strength propylene/butene copolymer and preparation method thereof |
| CN102816269A (en) * | 2011-06-09 | 2012-12-12 | 中国石油化工股份有限公司 | High-melt-strength propylene/ethylene copolymer and preparation method thereof |
| CN102816271A (en) * | 2011-06-09 | 2012-12-12 | 中国石油化工股份有限公司 | High-melt-strength propylene/ethylene/butene copolymer and preparation method thereof |
| CN103571044A (en) * | 2012-08-03 | 2014-02-12 | 中国石油化工股份有限公司 | Preparation method of high-impact-strength polypropylene kettle internal alloy |
| CN103788256A (en) * | 2012-10-30 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of high-melt fluidity high-rigidity antishock polypropylene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022221049A1 (en) * | 2021-04-15 | 2022-10-20 | Exxonmobil Chemical Patents Inc. | Processes for making improved polypropylene homopolymers, random copolymers, and impact copolymers |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105622809A (en) | 2016-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105622809B (en) | A kind of preparation method of the impact polypropylene of low VOC content | |
| CN105566533B (en) | A kind of low smell, low VOC content impact polypropylene preparation method | |
| EP1109842B9 (en) | Catalyst component comprising magnesium, titanium, a halogen and an electron donor, its preparation and use | |
| CN103788256B (en) | A kind of preparation method of high fluidity of molten high rigidity impact polypropylene | |
| CN102325809B (en) | Enhanced procatalyst composition and process | |
| EP1114072B1 (en) | Catalyst component comprising magnesium, titanium, a halogen and an electron donor, its preparation and use | |
| CN102481556B (en) | Cyclic organosilicon compounds as electron donors for polyolefin catalysts | |
| CN105829438A (en) | Process for producing propylene terpolymer | |
| EP2419213B1 (en) | Bicyclic organosilicon compounds as electron donors for polyolefin catalysts | |
| CN103788265B (en) | A kind of polyacrylic preparation method with high fondant-strength | |
| CN106488952B (en) | Polypropene composition | |
| EP3212705B1 (en) | Oxalic acid diamides as modifiers for polyolefin catalysts | |
| CN103360527A (en) | Preparation method and equipment of high-performance impact polypropylene | |
| CN103360528A (en) | Preparation method and equipment of high-performance impact polypropylene | |
| CN110997795B (en) | High stiffness polypropylene impact copolymers | |
| CN1444610A (en) | Highly flowable propylene block copolymers | |
| EP3683243B1 (en) | Process of manufacture of catalyst and propylene polymer that use this or copolymer for propylene polymerization | |
| CN101270172B (en) | High flow polypropylene polyalcohol catalyst system and application | |
| CN106459539A (en) | Propylene-based polymer composition | |
| CN101472681A (en) | Catalyst component for the polymerization of olefins | |
| CN105111357B (en) | Acrylic polymers and preparation method thereof | |
| CN112062885B (en) | Preparation method of high-rigidity heat-resistant polypropylene resin | |
| CN105330774B (en) | A kind of preparation method of wide steric regularity distribution polypropylene and obtained polypropylene | |
| CN114437264A (en) | Low-VOC low-odor polypropylene resin and preparation method and application thereof | |
| CN110382563A (en) | The method for being used to prepare the major catalyst for olefinic polymerization |
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 |