CN109679010A - A kind of preparation method of high impact resistance polypropylene - Google Patents
A kind of preparation method of high impact resistance polypropylene Download PDFInfo
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- CN109679010A CN109679010A CN201710976921.5A CN201710976921A CN109679010A CN 109679010 A CN109679010 A CN 109679010A CN 201710976921 A CN201710976921 A CN 201710976921A CN 109679010 A CN109679010 A CN 109679010A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
Abstract
The present invention provides a kind of polymerizations of high impact resistance polypropylene.It specifically includes: (1) the first excellent external electron donor of hydrogen response being added in endless tube propylene homo reactor in the first stage, to can be obtained the Noblen of high melt flow rate (MFR) under lower density of hydrogen；(2) second of external electron donor for helping to improve polypropylene isotacticity is added in the annular-pipe reactor of second stage, so that high-crystallinity polypropylene be prepared in the workshop section to assign material excellent rigidity；(3) second stage generate polymer surfaces spray attachment third external electron donor, enter it in the gas-phase reactor of phase III with polymer, thus the workshop section obtain sequence be evenly distributed, the higher propylene impact copolymers of content.
Description
Technical field
It is especially a kind of with high melt flow rate (MFR) the present invention relates to a kind of preparation method of high impact resistance polypropylene
The preparation method of high impact resistance polypropylene.
Background technique
High impact resistance polypropylene resin with high melt flow rate (MFR) (Gao Liudong), due to having than common impact copolymer
There is higher machine-shaping efficiency and have in injection molding art and be widely applied, market profit is also apparently higher than common crushing-resistant copolymerization
Object.Currently, the method for the high flowing high impact resistance polypropylene resin of preparation be broadly divided into that post-processing is modified and kettle in direct polymerization two it is big
Class.Post-processing modification, which refers to, carries out chain rupture processing in melt-processed for impact polypropylene resin obtained, drops its molecular weight
Low or molecular weight distribution broadens, to achieve the purpose that improve resin melt flowing rate.Although this method implementation steps are simple,
But since chain breaking process is to the homopolypropylene and copolymer polypropylene component non-selectivity in resin, thus cannot be to each component point
Son amount is regulated and controled respectively, optimize resin property can not；In addition, properties of product fluctuation is larger when processing conditions variation.
Direct polymerization method is directly realized by the design to resin molecular weight by adjusting polymerization technique parameter in a kettle in kettle, usually
A large amount of hydrogen (chain-transferring agent) is added in reaction kettle by using the catalyst system of specific function or using supercritical process
To reach regulation melt flow rate (MFR), the purpose of production high flow polypropylene resin.
Using the method for specific function catalyst, reported in Basell house journal CN1321178A, core
Technology is to prepare to have wide molecular weight point using ether compound as the Ziegler-Natta catalyst of internal electron donor using a kind of
The impact-resistant polyolefin resin of cloth.For another example patent CN1156999A has been invented containing there are two types of internal electron donor (tetraethoxysilanes
With Bicvclopentyl dimethoxysilane) catalyst system, the catalyst can be effectively prepared has provided higher melt flow speed
The polymer of rate wide molecular weight distribution in.But it is constrained to the unicity of above-mentioned catalyst function, is difficult to realize resin
High fluidity, the balance between rigidity and shock resistance three.
The preparation of high flowing copolymer also may be implemented by the adjusting to external electron donor, many patents are using mixing
The external electron donor of (two or more).Such as patent CN102532380A reports a kind of high fluidity punching proof acrylic preparation side
Method is closed in reaction by the propylene homo carried out at two sections and adds two kinds of different external electron donors of hydrogen response respectively, from
And widen the molecular weight distribution of polymer, the high flowing impact polypropylene that melt index is 25-100g/10min can be prepared.However
The disadvantages of this method is also very significant: the copolymerization effect due to being unable to control third section, product cannot be taken into account well
High fluidity and impact resistance improve mobility and then cause being remarkably decreased of impact property (polymer impact intensity is up to
28kJ/m2When, melt index only has 7.8g/10min).For another example patent CN102532381A reports a kind of with high melt flow
The preparation method of the impact copolymer of propylene of dynamic property, closes in propylene homo and a kind of external electron donor is used only in reaction, third
The second outer kind of electron donor is added when alkene is reacted with alpha-olefin copolymer, thus the propylene homopolymer component being respectively increased in product and
The mobility of copolymer component, but the disadvantage is that the composition and performance of copolymer can not be regulated and controled, in optimization product mobility
While can not promote impact property, impact strength is only 11.3kJ/m2.For another example, it is also mentioned in patent CN103788256A
The impact polypropylene of high flowing is prepared using the method for using different external electron donors, its main feature is that copolymerization stage is using propylene
Monomer and alpha-olefin copolymer (being using ethylene and alpha-olefin copolymer in usual technique), the resin being prepared has high flowing
Property, high rigidity, but poor (the only 15kJ/m of shock resistance2)。
Being analyzed by above-mentioned technology, which can be seen that, will prepare high flowing, the naval stores that rigidity is good, erosion-resisting characteristics is excellent,
Key factor (or difficult point) is how to realize the balance between three kinds of performances, rather than attends to one thing and lose sight of another.Realize high flowing, it is desirable that poly-
It closes in object and contains the polypropylene component that molecular weight is lower or molecular weight distribution is very wide；Realize high rigidity, it is desirable that contain in polymer
The polypropylene component of high isotactic (or high-crystallinity)；Realize high-impact, then require in polymer containing suitable content ethylene/
Alpha-olefin random copolymer, three are indispensable.And in current published technology, it cannot be considered in terms of above-mentioned three Xiang Xingneng.
Spheripol propylene polymerization process is the prevailing technology for preparing impact copolymer polypropylene, very widely used.Its skill
Art feature is to be carried out continuously polymerization technique process using three sections: including two sections of bulk propylene homopolymerizations and one section of gas phase copolymerization.
Thirdly the setting of segment process, to prepare high flowing proposed by the present invention, high rigidity, high impact resistance polypropylene provide possibility.
Summary of the invention
The present invention provides one kind directly to prepare on Spheripol polymerization technique has high flowing, high rigidity, high-impact
The polymerization process of the acrylic resin copolymer of performance.Specifically, the preparation method of copolymer polypropylene of the invention is to be directed to
The bicyclic pipe of Spheripol adds gas-phase reactor technology, in three concatenated reactors, progress one section of bulk polymerization of propylene, and two
Section bulk polymerization, the copolymerization of three sections of propylene and comonomer.
Method of the present invention specifically includes the following steps:
1) first stage: in hydrogen and in the presence of comprising the Ziegler-Natta catalyst system of the first external electron donor,
The liquid-phase bulk polymerization of propylene is carried out in the first annular-pipe reactor.
First external electron donor is selected from the compound that general formula is R1xR2ySi (OR3) z, and wherein R1 and R2 is respectively phase
Same or different C1-C3 linear paraffin bases, R3 are C1-C2 linear paraffin base, 0≤x < 2,0≤y < 2 and 0 < z≤4, specific choosing
From at least one of tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxysilane, dimethyl diethoxysilane,
It is preferred that tetraethoxysilane.
First stage propylene polymerization pressure is preferably 4000-4500KPa, under 70-80 DEG C of polymerization temperature, obtains high stream
Dynamic Noblen.
The Ziegler-Natta catalyst system specifically includes that component (1) is a kind of with magnesium, titanium, halogen and interior to electricity
Daughter is the ingredient of solid catalyst and a kind of organo-aluminium component of component (2) of main component；(3) first external electron donor of component；
Wherein with titanium/aluminum meter, the ratio of component (1) and component (2) organo-aluminum compound is 1:10~1:500；Preferably 1:25
~1:100.Wherein the mass ratio of the organo-aluminium component and the first external electron donor component is 1~50, preferably 2~20.
Ingredient of solid catalyst is that the prior art is common in Zigler-Natta catalyst system of the present invention
Main catalyst for propylene polymerization, the component (1) can be used CN85100997, CN98126385.2, CN00109216.2,
Catalyst disclosed in CN99125567.4, CN201210077908.3, CN201310552108.7 is literary using these patents
Disclosed preparation method is offered to obtain.The present invention provides a kind of preparation method of preferred component (1), specifically comprises the following steps:
A) at -15 DEG C~-20 DEG C, spherical magnesium halide carrier is added in liquid titanium compound, the molar ratio of Ti/Mg
It is 20~40, best 25~30, low-temp reaction 1h~2h；
B) 60 DEG C~80 DEG C are warming up to, internal electron donor compound is added, internal electron donor compound described here is such as
Usually used phthalate compound, succinate compound compound, diether compound etc., preferably phthalic acid
Ester type compound.The molar ratio of internal electron donor and magnesium halide continues to be warming up to 120 DEG C of reaction 2h 0.01~0.20；
C) liquid is filtered off, rejoins fresh liquid titanium compound, the molar ratio of Ti/Mg is 20~40, best
25~30, in 120 DEG C of reaction 2h；
E) liquid is filtered off, obtains the component (1) through n-hexane washing, vacuum drying.
Cocatalyst component (2) of the present invention is organo-aluminum compound, optimizing alkyl aluminium compound, more preferably three alkane
Base aluminium.
2) second stage: first stage polymerizate enters the second annular-pipe reactor, in hydrogen and the second external electron donor
In the presence of carry out liquid phase bulk propylene polymerization；
Second external electron donor is selected from the compound that general formula is R1xR2ySi (OR3) 2, and wherein R1 is C4-C10 branch
Alkyl or cyclic alkane base, R2 are C1-C10 branched alkane alkyl or cyclic alkane base, and R3 is C1-C2 linear paraffin base, wherein 1
≤ x≤2,0≤y < 2 are chosen in particular from dicyclopentyl dimethoxyl silane (DCPMS), Cyclohexyl Methyl Dimethoxysilane, two different
At least one of butyldimethoxysilane, di-t-butyl dimethoxysilane, preferably dicyclopentyl dimethoxyl silane.
Second stage propylene polymerization temperature is 70-80 DEG C, polymerization pressure 4000-4500KPa, second stage
Reaction generates the macromolecular skeleton having compared with high isotactic.
The wherein mass ratio 1~100 of the organo-aluminium component and second external electron donor, preferably 5~30.
3) phase III: the polymer product of second stage removes unreacted propylene monomer and hydrogen by high pressure flash vessel
After gas, into gas-phase reactor, a mouth is set in the connecting pipe of high pressure flash vessel and gas-phase reactor, will be given outside third
Connecting pipe is added by the branch mouth in electron, and an atomizer is housed on branch mouth, and third external electron donor passes through atomization spray
Mouth, uniform spray attachment polymerize produce on the second stage polymer product surface for flowing through connecting pipe, with the second stage
Object enters gas-phase reactor together, carries out copolyreaction.
The third external electron donor is selected from diether compound.The diether compound has as led to formula (I) institute
Show structural formula.
R, R in formulaI、RII、RIII、RIVAnd RVIt is same or different, be hydrogen or linear containing 1~18 carbon atom or
Alkyl, naphthenic base, aryl, alkylaryl or the aryl alkyl of branching, and R, RIIt cannot simultaneously be H or CH3；RVIAnd RVII
It is same or different, it is the linear or branched-alkyl containing 1~18 carbon atom, preferably methyl.
The diether compound is chosen in particular from 2,2- diphenyl -1,3- dimethoxy propane, di-t-butyl -1 2,2-,
3- di ethyl propyl ether, -1,3 dimethoxy propane of 2- methyl -2- ethyl, -1,3 dimethoxy propane of 2- methyl -2- tert-butyl,
2,2- di-t-butyl -1,3- dimethoxy propane, -1,3 dimethoxy propane of 2- methyl -2- cyclohexyl etc..It is preferred that bis- uncle of 2,2-
Butyl -1,3- dimethoxy propane.
Reaction temperature is 80-90 DEG C in phase III gas-phase reactor, reaction pressure 1200-1300KPa.
The mass ratio 1~100 of the organo-aluminium component and third external electron donor component, preferably 5~30.
Comonomer described in the phase III is ethylene or butylene, when combined polymerization, according to properties of product needs, adjustment
The ratio of each monomer when gas-phase polymerization, when comonomer is ethylene, usually control ethylene/(ethylene+propylene) is 0.25-0.41
(molar ratio), preferably 0.32-0.38 (molar ratio), while hydrogen content therein is controlled, obtain target product.
The present invention utilizes Spheripol polymerization technique, realizes the high flowing, high rigidity, highly resistance of propylene copolymer resins
Balance between punching property three, specific method can be summarized as: be directed to above-mentioned three kinds of performances, be respectively adopted three kinds it is different outer to electricity
They, are used three different workshop sections in Spheripol technique by daughter respectively, i.e. the endless tube propylene of (1) in the first stage is equal
The first excellent external electron donor of hydrogen response is added in poly- reactor, to can be obtained under lower density of hydrogen
The Noblen of high melt flow rate (MFR)；(2) it is added in the annular-pipe reactor of second stage and helps to improve polypropylene etc.
Second of external electron donor of normality, so that high-crystallinity polypropylene be prepared in the workshop section to assign material excellent rigidity；
(3) the polymer surfaces spray attachment third external electron donor generated in second stage, makes it enter the phase III with polymer
In gas-phase reactor, thus the workshop section obtain sequence be evenly distributed, the higher propylene impact copolymers of content.Inventor passes through
The Lewis alkalinity sequence of repetition test discovery, these three external electron donors must be: the third > second > the first is outer to electricity
Daughter, so that making the copolymer polypropylene finally prepared not only has high melt flow rate (MFR), there are also very high shock resistance,
Excellent rigidity is had both simultaneously.
On the basis of the Noblen for generating high melt flow rate (MFR) in the first stage, the propylene for carrying out second stage is equal
Poly-, the second external electron donor that Lewis alkalinity is better than the first external electron donor need to be separately added in second stage, and hydrogen can be added on a small quantity
Gas generates the high macromolecular polypropylene backbone of isotacticity.Before the homopolypropylene that second reactor comes out enters gas-phase reactor,
The third external electron donor need to separately be added, carry out propylene and alpha-olefin copolymer, the additional amount of adjustment comonomer composition controls rubber
The composition and content of glue phase, then the melt flow rate (MFR) of the amount control final product by adjusting hydrogen.
Wherein the productivity ratio of first reactor, second reactor and third reactor is controlled in 10:50:40~20:60:
20, preferably 15:55:30~12:53:35.
Present invention is generally directed to the bicyclic pipes of Spheripol to add gas-phase reactor technology, and three step polymerization reactions are respectively at three
It is carried out in reactor, in the first stage in polymerization reaction, three kinds of catalytic components can be added directly into first reactor,
It may also pass through industry to know pre- complexing and/or pre-polymerization altogether and then be added in first reactor.The purpose of the pre- complex reaction is
Enable the sufficiently effective mixing of catalyst components, can be continuous stirred tank reactor, annular-pipe reactor etc..The temperature being complexed in advance
It can be controlled between -10~60 DEG C, preferably 10-30 DEG C.The time being complexed in advance controls in 30~100min, preferably 5~30min.
Bulk propylene or slurry prepolymerization can be also carried out with or without the catalyst being complexed in advance.It can be continuous
It being carried out in blender or annular-pipe reactor, prepolymerized temperature control is between -10~60 DEG C, and preferably 10-30 DEG C.It is prepolymerized
Multiple is controlled at 30-300 times, and preferably 50-150 times.
First stage bulk propylene polymerization is carried out in the first annular-pipe reactor of Spheripol technique, polymerization temperature
It is 70-80 DEG C, polymerization pressure is in 4000-4500KPa.
Second stage bulk propylene polymerization is carried out in the second annular-pipe reactor of Spheripol technique, polymerization temperature
It is 70-80 DEG C, polymerization pressure is in 4000-4500KPa.
Phase III propylene with the conjunction of comonomer alpha-olefin copolymer is carried out in the gas-phase reactor of Spheripol technique
, reaction temperature is 75-80 DEG C, reaction pressure 1200-1300KPa.Alpha-olefin as comonomer is ethylene or butylene, preferably second
Alkene.When comonomer is ethylene, usually control ethylene/(ethylene+propylene) is 0.25-0.41 (molar ratio), preferably 0.32-
0.38 (molar ratio).
The polymer that preparation method of the present invention obtains can be used polyolefin commonly used equipment and carry out extruding pelletization, and when granulation adds
Enter the auxiliary agent that this field is usually added, such as antioxidant, light stabilizer, nucleating agent.
Polymerization of the invention is especially suitable in Spheripol technique, preparation has high melt flow rate (MFR) and Gao Chong
The copolymer polypropylene product of hit intensity is particularly suitable for melt flow rate (MFR) greater than 30g/10min, and notch impact strength is greater than 40kJ/
m2Impact copolymer polypropylene product.Only by external electron donor type, dosage and the density of hydrogen for adjusting each stage of reaction.
Under the conditions of the Ziegler-Natta catalyst of general performance, so that it may which it is total that direct polymerization obtains high performance anti-impact
Poly- polypropylene product, the copolymerized product of this kind of performance, generally requiring could be prepared by gas-phase polymerization process.The present invention does not need spy
Different high-cost catalyst activity component carries out controlled degradation without to product.Cost is relatively low, and existing big device is easy to operate,
Easily implement, can effectively solve the technical bottleneck of the flowing of Spheripol process exploitation height, high-impact, high rigidity copolymer polypropylene product.
This method is suitable in double loop reactor and single gas phase kettle (or double gas phase kettles) concatenated Spheripol technique
Produce the acrylic resin that melt index (MI) is high, rigidity is good, erosion-resisting characteristics is excellent.
Specific embodiment
Embodiment
Below will by specific embodiment, the present invention will be described in detail, preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
The related data of polymer are obtained by following test method in embodiment:
1. melt flow rate (MFR) (MFR): according to ISO1133,230 DEG C, measuring under 2.16kg load.
2. bending modulus: being measured by ASTM D790-97.
3. Izod impact strength: being measured by ASTM D256-00.
4. polymer ethylene content measures: infrared (IR) method measurement.
5. polymer xylene soluble content measures: pressing ASTM D5492.
Embodiment 1
Major catalyst (the solid catalyst activity component of titaniferous) is retouched using 201310552108.7 embodiment 1 of Chinese patent
The method stated obtains, Ti content: 2.76%, content of magnesium: and 18.0%, diisobutyl phthalate content: 7.54%.Polymerization
Monomer is propylene and ethylene.
Polymerization reaction carries out on the bicyclic Guan Jiadan gas-phase reactor device of Spheripol.
Prepolymerization: major catalyst, co-catalyst (triethyl aluminum), the first external electron donor (tetraethoxysilane) are 10
DEG C, after pre-contact 20min, the continuous prepolymerization reactor that is added carries out pre-polymerization reactor, into the triethyl group of prepolymerization reactor
Aluminium (TEA) flow is 6.33g/hr, and tetraethoxysilane (the first external electron donor, Donor-A) flow is 0.63g/hr, main reminder
Agent flow is 0.01g/hr.Wherein, TEA/Donor-A mass ratio is 10.Prepolymerization carries out under propylene liquid-phase bulk environment,
Temperature is 15 DEG C, residence time 4min, and the pre-polymerization multiple of catalyst is about 120-150 times under this condition.
Slurries after prepolymerization continuously enter the first annular-pipe reactor, and high melt flows are completed in the first annular-pipe reactor
The preparation of rate homopolypropylene, polymeric reaction temperature are 70 DEG C, reaction pressure 4.0MPa, are added in the first annular-pipe reactor
The hydrogen (gas chromatographic detection) of 7000ppm.Due to major catalyst and co-catalyst and the first external electron donor (Donor-A)
Have already passed through pre-contact and prepolymerization and enter the first annular-pipe reactor, thus in the first annular-pipe reactor except propylene and hydrogen into
Material is outer, without adding entering any ingredient.
Slurries after the first annular-pipe reactor continuously enter the second annular-pipe reactor, and polymeric reaction temperature is 70 DEG C,
Reaction pressure is 4.0MPa, and the hydrogen (gas chromatographic detection) of 1000ppm is added in the second annular-pipe reactor.And in the second ring
The second external electron donor dicyclopentyl dimethoxyl silane (Donor-B) is added in supplement in pipe reactor, completes high isotactic
The polyacrylic preparation of macromolecular skeleton.Wherein TEA/Donor-B mass ratio is 11.
Slurries after the second annular-pipe reactor continuously enter the gas fluidized bed reactor with expanding reach, carry out second
The copolymerization of alkene and propylene, reaction temperature are 75 DEG C, reaction pressure 1.2MPa, usually control ethylene/(ethylene+propylene)
For 0.375 (molar ratio), appropriate amount of hydrogen is separately added in gas-phase reactor, on-line chromatograph detects hydrogen/(second in gas-phase reactor
Alkene+propylene) it is 1.1%, supplement the third external electron donor 2 of addition, 2- di-t-butyl -1,3- dimethoxy propane (Donor-
C it) is added in the second annular-pipe reactor outlet section, wherein TEA/Donor-C mass ratio is 12.
Concrete technology condition is shown in Table 1.
The final product obtained after gas-phase reactor is passing through drier, is obtaining polymer powders after the processing of deactivation tank.
Polymer powders be added 0.05% 1010,0.1% 168 and 0.05% calcium stearate, after mixing,
Extruding pelletization, pellet be tested for the property by existing related ASTM standard.The performance test results are shown in Table 2.
Embodiment 2
Embodiment 2 is identical as 1 process of embodiment to embodiment 6, only each component additional amount different from, is specifically shown in Table 1 institute
Show, performance test is shown in Table 2.
Embodiment 7
Embodiment 7 is identical as 1 process of embodiment to embodiment 8, and wherein major catalyst selects commercially available CS-II ball-type magnesium chloride
Carried catalyst, each component additional amount different from polymerization process, is specifically shown in Table 1, performance test is shown in Table 2.
Comparative example 1
A kind of external electron donor dicyclopentyl dimethoxyl silane is only added in the first annular-pipe reactor in comparative example 1,
Without adding external electron donor in second annular-pipe reactor and gas-phase reactor, other conditions are the same as embodiment 1.Concrete technology condition
It is shown in Table 1, the performance test results are shown in Table 2.
Comparative example 2
The first external electron donor tetraethoxysilane, the second endless tube is added in comparative example 2 in the first annular-pipe reactor
Second of external electron donor dicyclopentyl dimethoxyl silane is added in reactor, no longer separately adds outer electron in gas-phase reactor
Body, other conditions are the same as embodiment 2.Concrete technology condition is shown in Table 1, and the performance test results are shown in Table 2.
Comparative example 3
External electron donor dicyclopentyl dimethoxyl silane, the second ring is added in comparative example 3 in the first annular-pipe reactor
Without adding external electron donor in pipe reactor, external electron donor 2,2- di-t-butyl -1,3- dimethoxy are added in gas-phase reactor
Base propane, other conditions are the same as embodiment 3.Concrete technology condition is shown in Table 1, and the performance test results are shown in Table 2.
Comparative example 4
External electron donor tetraethoxysilane, the second annular-pipe reactor is added in comparative example 4 in the first annular-pipe reactor
And without adding external electron donor in gas-phase reactor, other conditions are the same as embodiment 4.Concrete technology condition is shown in Table 1, performance test knot
Fruit is shown in Table 2.
Comparative example 5
Dicyclopentyl dimethoxyl silane is added in comparative example 5 in the first annular-pipe reactor, in the second annular-pipe reactor
Without adding external electron donor, 2,2- di-t-butyl -1,3- dimethoxy propane external electron donor is added in gas-phase reactor, it is other
Condition is the same as embodiment 5.Concrete technology condition is shown in Table 1, and the performance test results are shown in Table 2.
Comparative example 6
Type and content condition is added with embodiment 6 in 6 each component of comparative example, the difference is that third external electron donor
Adding manner is importing directly into polymer powder by measuring pipeline by being changed to by atomizer spray attachment on homopolymer powder surface
In material, concrete technology condition is shown in Table 1, and the performance test results are shown in Table 2.
Comparative example 7
Comparative example 7 is same as Example 7, the difference is that third external electron donor adding manner is by passing through in gas phase kettle
Atomizer spray attachment is changed to be importing directly into polymer powders by measuring pipeline on homopolymer powder surface, concrete technology item
Part is shown in Table 1, and the performance test results are shown in Table 2.
Comparative example 8
Comparative example 8 is same as Example 8, the difference is that third external electron donor adding manner is by passing through in gas phase kettle
Atomizer spray attachment is changed to be importing directly into polymer powders by measuring pipeline on homopolymer powder surface, concrete technology item
Part is shown in Table 1, and the performance test results are shown in Table 2.
1 embodiment of table and comparative example concrete technology condition
Data in analytical table 1, table 2 can see, and comparative example 2 and comparative example 1 are added different by three-step approach
External electron donor is compared with single external electron donor preparation copolymer polypropylene is added in one-step method, the melt flow rate (MFR) of product, punching
It hits performance and is much higher than the latter.Comparative example 2 and comparative example 2, by three-step approach be added different external electron donor with it is bicyclic
Pipe, which is added, to be added without specific external electron donor in different external electron donors but gas phase kettle and compares, the former impact property is significantly high
In the latter, and the former comprehensive performance is also superior to the latter.Comparative example 2 and comparative example 3 are added different outer by three-step approach
Electron donor and the first annular-pipe reactor and gas-phase reactor are added different external electron donors, the second annular-pipe reactor without adding
External electron donor is compared, and the bending modulus (rigidity) of the former product is better than the latter.Comparative example 2 and comparative example 4, pass through three steps
Different external electron donors is added compared with a kind of external electron donor tetraethoxysilane is only added in entire reaction process in method, the former
Comprehensive performance bending modulus, impact property is far superior to the latter.Comparative example 2 and comparative example 5 are added not by three-step approach
Different external electron donors, the second annular-pipe reactor is added from the first annular-pipe reactor and gas-phase reactor in same external electron donor
It is compared without adding external electron donor, the former melt flow rate (MFR) will be far superior to the latter.Comparative example 2 and comparative example 6 are led to
Cross the impact for the product for being prepared third external electron donor (copolymerized ability is strong) spray attachment on homopolymer powder surface by atomizer
Performance is much better than the product that third external electron donor is importing directly into polymer powders by measuring pipeline, because passing through atomization
The mode third external electron donor of nozzle spray attachment more uniform dispersion and can be diffused in polymer powders.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to the protection scope of the claims in the present invention.
Claims (15)
1. a kind of polymerization of high impact resistance polypropylene, which is characterized in that specifically includes the following steps:
1) first stage: in hydrogen and in the presence of comprising the Ziegler-Natta catalyst system of the first external electron donor,
The liquid-phase bulk polymerization of propylene is carried out in one annular-pipe reactor；It is R1xR2ySi that first external electron donor, which is selected from general formula,
(OR3) compound of z, wherein R1 and R2 is respectively same or different C1-C3 linear paraffin base, and R3 is C1-C2 straight chain alkane
Alkyl, 0≤x < 2,0≤y < 2 and 0 < z≤4；
2) second stage: first stage polymerizate enters the second annular-pipe reactor, exists in hydrogen and the second external electron donor
Lower carry out liquid phase bulk propylene polymerization；Second external electron donor is selected from the compound that general formula is R1xR2ySi (OR3) 2,
Middle R1 is C4-C10 branched alkane alkyl or cyclic alkane base, and R2 is C1-C10 branched alkane alkyl or cyclic alkane base, R3 C1-C2
Linear paraffin base, wherein 1≤x≤2,0≤y < 2；
3) phase III: the polymer product of second stage removes unreacted propylene monomer and hydrogen by high pressure flash vessel
Afterwards, into gas-phase reactor, third external electron donor is added in the connecting pipe of high pressure flash vessel and gas-phase reactor, institute
The third external electron donor stated is selected from diether compound.
2. preparation method as described in claim 1, which is characterized in that in the connecting pipe of high pressure flash vessel and gas-phase reactor
The connecting pipe is added by the branch mouth in third external electron donor by one mouth of upper setting.
3. preparation method as claimed in claim 2, which is characterized in that an atomizer is housed on the branch mouth, is given outside third
Electron is by atomizer, and spray attachment is on the second stage polymer product surface for flowing through connecting pipe, with described second
Stage polymer product enters gas-phase reactor together.
4. preparation method as described in claim 1, which is characterized in that the Lewis alkalinity sequence of three kinds of external electron donors
Meet following relationship: third external electron donor > the second external electron donor > the first external electron donor.
5. preparation method as described in claim 1, which is characterized in that the first stage propylene polymerization pressure is 4000-
4500KPa, polymerization temperature are 70-80 DEG C.
6. preparation method as described in claim 1, which is characterized in that the Ziegler-Natta catalyst system includes:
Component (1) is a kind of to be had by the ingredient of solid catalyst of main component and component (2) one kind of magnesium, titanium, halogen and internal electron donor
Machine aluminium component；(3) first external electron donor of component；Wherein with titanium/aluminum meter, component (1) and component (2) organo-aluminum compound
Ratio be 1:10~1:500；Preferably 1:25~1:100；Wherein the organo-aluminium component and the first external electron donor component
Mass ratio be 1~50, preferably 2~20.
7. preparation method as described in claim 1, which is characterized in that the organo-aluminium group is divided into alkyl aluminum compound.
8. preparation method as described in claim 1, which is characterized in that the second stage propylene polymerization temperature is 70-
80 DEG C, polymerization pressure 4000-4500KPa.
9. preparation method as described in claim 1, which is characterized in that the organo-aluminium component and the described second outer electron
The mass ratio of body is 1~100, preferably 5~30.
10. preparation method as described in claim 1, which is characterized in that the diether compound has as shown in logical formula (I)
Structural formula:
R, R in formulaI、RII、RIII、RIVAnd RVIt is same or different, it is hydrogen or the linear or branching containing 1~18 carbon atom
Alkyl, naphthenic base, aryl, alkylaryl or aryl alkyl, and R, RIIt cannot simultaneously be H or CH3；RVIAnd RVIIIt is identical
Or it is different, it is the linear or branched-alkyl containing 1~18 carbon atom, preferably methyl.
11. preparation method as claimed in claim 1 or 7, which is characterized in that the diether compound is selected from 2,2- hexichol
Base -1,3- dimethoxy propane, 2,2- di-t-butyl -1,3- di ethyl propyl ether, -1,3 dimethoxy third of 2- methyl -2- ethyl
Alkane, -1,3 dimethoxy propane of 2- methyl -2- tert-butyl, 2,2- di-t-butyl -1,3- dimethoxy propane, 2- methyl -2- ring
Hexyl -1,3 dimethoxy propane, preferably 2,2- di-t-butyl -1,3- dimethoxy propane.
12. preparation method as described in claim 1, which is characterized in that react temperature in the phase III gas-phase reactor
Degree is 80-90 DEG C, reaction pressure 1200-1300KPa.
13. preparation method as described in claim 1, which is characterized in that the organo-aluminium component and third external electron donor
The mass ratio of component is 1~100, preferably 5~30.
14. preparation method as described in claim 1, which is characterized in that first external electron donor is selected from tetramethoxy-silicane
At least one of alkane, tetraethoxysilane, methyltrimethoxysilane, dimethyl diethoxysilane.
15. preparation method as described in claim 1, which is characterized in that second external electron donor is selected from bicyclopentyl two
Methoxy silane, Cyclohexyl Methyl Dimethoxysilane, second, isobutyl dimethoxy silane, in di-t-butyl dimethoxysilane
At least one.
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