CN105623075B - A kind of preparation method of the impact polypropylene material of high fondant-strength - Google Patents
A kind of preparation method of the impact polypropylene material of high fondant-strength Download PDFInfo
- Publication number
- CN105623075B CN105623075B CN201410602299.8A CN201410602299A CN105623075B CN 105623075 B CN105623075 B CN 105623075B CN 201410602299 A CN201410602299 A CN 201410602299A CN 105623075 B CN105623075 B CN 105623075B
- Authority
- CN
- China
- Prior art keywords
- ethylene
- noblen
- dimethoxysilane
- propylene homopolymer
- electron donor
- 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 the impact polypropylene material of high fondant-strength, propylene homo being carried out in the presence of the first Noblen, the propylene homopolymer component comprising the first Noblen and the second Noblen being obtained by the reaction, 1 butene of ethylene is then carried out in the presence of the propylene homopolymer component is obtained by the reaction the polypropylene material for including 1 butylene copolymer of ethylene.By using the external electron donor for using different type and dosage respectively in different polymerization stages, in conjunction with the different amounts of chain-transferring agent hydrogen, prepare the homopolypropylene continuous phase of extremely wide molecular weight distributions with particular melt index, containing a large amount of super high molecular weight components, and the combined polymerization of ethylene and 1 butylene is further carried out on this basis, obtain being scattered in the rubber phase in continuous phase, and then the impact polypropylene material with high fondant-strength, high rigidity and high tenacity is obtained, it is widely used.
Description
Technical field
The present invention relates to the preparation methods of polypropylene material, and in particular to a kind of impact polypropylene material of high fondant-strength
Preparation method.
Background technology
Impact polypropylene have the rigidity such as excellent high/low temperature impact strength, higher tensile strength, bending modulus with
And higher heat resisting temperature, it is had been widely used in many fields, such as molding or the automobile component of extrusion molding, appliances parts, appearance
Device and household items etc..Impact polypropylene commonly used in injection processing, and is used for blow molding since its melt strength is relatively low
When, there are mold base size is unstable, products thickness uneven the problems such as can not being even molded.
Improve melt strength of polypropylene common way be reduce melt index, i.e. raising polypropylene molecule amount, but this
Material molten can be brought and squeezed out difficult.Still an alternative is that widening molecular weight distribution, such as US7365136 and US6875826
Report it is a kind of prepare wide molecular weight distribution, the method for high fondant-strength homopolymerization and atactic copolymerized polypropene, select alkoxy
Silane is external electron donor (such as dicyclopentyl dimethoxyl silane), dense by adjusting hydrogen in multiple concatenated reactors
Degree comes regulatory molecule amount size and distribution, realizes the effect for improving melt strength of polypropylene.WO9426794 discloses multiple strings
The method that the reactor of connection prepares high fondant-strength homopolymerization and random polypropylene, by adjust different reactor in hydrogen it is dense
It spends to prepare the high melt strength, propylene of wide molecular weight distribution or bimodal distribution, the property of catalyst is not done in each reactor
Adjustment, thus preparation process needs a large amount of hydrogen.
CN102134290 and CN102134291 discloses a kind of wide molecular weight distribution, high fondant-strength homopolypropylene
Preparation method, use multiple tandem reactors by control external electron donor component the differential responses stage type and ratio
Example is prepared for wide molecular weight, high fondant-strength homopolypropylene or random in conjunction with the control of molecular weight regulator hydrogen usage
Copolymer polypropylene.
China applies for a patent 201210422726.5 it is also reported that two distinct types of outer by silanes and two ethers
The regulation and control of isotactic index and hydrogen response between catalyst different reactor are realized in the reasonably combined of electron donor, are obtained
To the preparation method with wide molecular weight distribution, high fondant-strength homopolypropylene or random polypropylene.
Above-mentioned patent report is high fondant-strength homopolypropylene or the preparation method of atactic copolymerized polypropene, that is,
Say, homopolypropylene or the atactic copolymerized polypropene being prepared by these methods although having higher melt strength,
It is that rigidity, toughness or erosion-resisting characteristics are insufficient, to limit obtained polyacrylic application.Therefore it provides having rubber group
Divide and the impact polypropylene and preparation method thereof of the high fondant-strength of rubber disperse phase structure, high rigidity and toughness there will be weight
Big meaning.
Invention content
The present inventor provides a kind of preparation of the intensity impact polypropylene material of high melt by further investigation
Method, the polypropylene material being prepared by this method while also having the characteristics that high rigidity and high tenacity.The polypropylene material
It is the excellent material for being suitable for the fields such as automobile component, medical instrument, household items.
According to the present invention, a kind of method preparing high fondant-strength impact polypropylene material as described above is provided, is wrapped
It includes：
The first step：Propylene homo reacts, including：
First stage：Under the action of the Ziegler-Natta catalyst comprising the first external electron donor, exist in hydrogen
Propylene homo reaction is carried out in the absence of or, obtains the reaction stream for including the first Noblen；
Second stage：The second external electron donor is added and carries out complex reaction with the catalyst in the reaction stream, then
Propylene homo reaction is carried out in the presence of the first Noblen and hydrogen, generates the second Noblen, is obtained comprising the
The propylene homopolymer component of one Noblen and the second Noblen；Wherein,
First Noblen and the propylene homopolymer component measure molten under 230 DEG C, the load of 2.16kg
It is respectively 0.001-0.4g/10min and 0.1-15g/10min to melt index；
Second step：Ethylene -1- butenes react, and are included in the presence of the propylene homopolymer component and hydrogen and carry out
Ethylene -1- butylene gas phase copolymerizations generate ethylene-butene-1 copolymer component, obtain including the propylene homopolymer component
With the polypropylene material of ethylene-butene-1 copolymer (Ethylene/1-butene copolymer) component.
In method provided by the invention, propylene homopolymer component is first prepared as continuous phase, is provided for polypropylene material
Certain rigidity, then prepared on the basis of propylene homopolymer component ethylene-butene-1 copolymer component as rubber phase, i.e.
Dispersed phase can improve the toughness of polypropylene product.
In the first phase, the dosage of hydrogen for example can be 0-200ppm.In second stage, the dosage of hydrogen is
2000-20000ppm。
Method provided by the invention preferably carries out in the reactor of two or more serial operations.
It is the method for the direct catalytic polymerization of Ziegler-Natta catalyst according to the method for the present invention.By using going here and there
Two or more different types of external electron donors are used in multiple reactors of connection respectively, suitable external electron donor is selected to use
Amount, the dosage of different chain-transferring agent hydrogen in association reaction, prepare it is with particular melt index, contain a large amount of supra polymers
Measure the homopolypropylene continuous phase of the extremely wide molecular weight distribution of component.It is preferred that the molecular weight distribution M of the homopolymerization componentw/Mn(weight
Average molecular weight/number-average molecular weight)=6-20, the content that molecular weight is more than 5,000,000 fractions is greater than or equal to 1.5 weight %, and small
In or equal to 5 weight %；The content that molecular weight is less than 50,000 fractions is greater than or equal to 15.0 weight %, and is less than or equal to 40 weights
Measure %；Mz+1/Mn((Z+1)-average molecular weight/number-average molecular weight) is greater than or equal to 70, and is less than 150.And on this basis further
The combined polymerization for carrying out ethylene and 1- butylene, obtains being scattered in the rubber phase in continuous phase, by the reaction item for controlling copolyreaction
Part obtains the impact polypropylene material with high fondant-strength effect composition, structure and the content etc. that control rubber phase.
In method provided by the invention, used catalyst is Ziegler-Natta catalyst, preferably has Gao Li
The catalyst of structure selectivity.The Ziegler-Natta catalyst of high stereoselective described herein refers to that can be used for preparing
The catalyst of Noblen of the isotactic index more than 95%.This kind of catalyst usually contains the solid catalysis of (1) titaniferous
Agent active component, main component are magnesium, titanium, halogen and internal electron donor；(2) organo-aluminum compound cocatalyst component；(3)
External electron donor component.
Solid catalyst activity component in the method for the present invention in the Ziegler-Natta catalyst that uses (and can claim
Major catalyst) can be well known in the art.It is available this kind of to contain the specific of active solid catalyst component (1)
Example see, for example, patent document CN85100997, CN98126383.6, CN98111780.5, CN98126385.2,
In CN93102795.0, CN00109216.2, CN99125566.6, CN99125567.4 and CN02100900.7.These patents
The full content of document is incorporated by reference into the present invention.
Organo-aluminum compound optimizing alkyl calorize in the Ziegler-Natta catalyst used in the method for the present invention is closed
In object, more preferably trialkylaluminium, for example, triethyl aluminum, triisobutyl aluminium, three n-butylaluminums and three hexyl aluminium etc. at least
It is a kind of.
The active solid catalyst component of titaniferous in the method for the present invention in the Ziegler-Natta catalyst that uses and
The molar ratio of organo-aluminum compound is calculated as 10 with aluminium/titanium:1~500:1, preferably 25:1~100:1.
According to the present invention, it is R that first external electron donor, which is preferably selected from general formula,1R2Si(OR3)2Compound in extremely
Few one kind；Wherein, R2With R1It is each independently selected from C1-C6Linear or branched alkyl group, C3-C8Naphthenic base and C5-C12Heteroaryl,
R3For C1-C3Straight chain aliphatic.Specific example includes but are not limited to methyl-cyclopentyl-dimethoxysilane, ethyl-ring penta
Base-dimethoxysilane, n-propyl-cyclopenta-dimethoxysilane, two (2- methyl butyls)-dimethoxysilanes, two (3-
Methyl butyl)-dimethoxysilane, 2- methyl butyls -3- methyl butyls-dimethoxysilane, two (2,2- dimethyl-the third
Base)-dimethoxysilane, 2- methyl butyls -2,2- Dimethyl-propyls-dimethoxysilane, 3- methyl butyl -2,2- diformazans
Base-propyl-dimethoxysilane dimethyldimethoxysil,ne, dimethyl diethoxysilane, diisobutyl dimethoxy silicon
Alkane, methylcyclohexyl dimethoxy silane, methyl-isobutyl dimethoxysilane, Dicyclohexyldimethoxysilane, methyl-isopropyl
Base dimethoxysilane, isopropyl-cyclopenta dimethoxysilane, dicyclopentyl dimethoxyl silane, isopropyl-isobutyl group two
Methoxy silane, diisopropyl dimethoxy silane etc..
The molar ratio of the organo-aluminum compound and the first external electron donor is calculated as 1 with aluminium/silicon:1~100:1, preferably
10:1~60:1.
In the method according to the invention, including the catalyst of the first external electron donor can be added directly into homopolymerization
In device, the known pre-contact of industry and/or prepolymerization can also be passed through and then be added in homopolymerization device.The pre-polymerization
Conjunction refers to the prepolymerization that catalyst carries out certain multiplying power at a lower temperature, 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 is usually -10~50 DEG C, preferably 5~30 DEG C.Pre-contact step is optionally set before prepolymerization technology
Suddenly.The pre-contacting steps refers to co-catalyst in catalyst system, external electron donor and major catalyst (solid active central set
Point) carry out catalyst system complex reaction, with obtain with polymerization activity catalyst system.The temperature of pre-contacting steps is logical
Often control is -10~50 DEG C, preferably 5~30 DEG C.
According to the present invention, second external electron donor is selected from the chemical combination as shown in chemical general formula (I), (II) and (III)
At least one of object；
Wherein R1And R2It is each independently selected from C1-C20One kind in straight chain, branched or cricoid aliphatic group, R3、
R4、R5、R6、R7And R8It is each independently selected from hydrogen atom, halogen atom, C1-C20Linear or branched alkyl group, C3-C20Naphthenic base,
C6-C20Aryl, C7-C20Alkaryl and C7-C20One kind in aralkyl；R9、R10And R11It is each independently C1-C3Linear aliphatic
Group, R12For C1-C6Linear or branched alkyl group or C3-C8Naphthene group.The specific example of second external electron donor includes but not only
It is limited to 2,2- diisobutyl -1,3- dimethoxy propanes, 2,2- phenyl -1,3- dimethoxy propanes, 2,2- benzyls -1,3- two
Bis- (the cyclohexyl methyl) -1,3- dimethoxys of methoxy propane, 2- isopropyl -2- isopentyl -1,3- dimethoxy propanes, 2,2- third
Alkane, 2- isopropyls -2-3,7- dimethyl octyls-dimethoxy propane, 2,2- isopropyl -1,3- dimethoxy propanes, 2- isopropyls -
2- cyclohexyl methyl -1,3- dimethoxy propanes, 2,2- diisobutyl -1,3- di ethyl propyl ethers, 2,2- diisobutyls -1,3- two
Propoxyl group propane, 2- isopropyl -2- isopentyl -1,3- di ethyl propyl ethers, 2- isopropyl -2- isopentyl -1,3- dipropoxies
Bis- (the cyclohexyl methyl) -1,3- di ethyl propyl ethers of propane, 2,2-, n-propyl triethoxysilane, isopro-pyltriethoxysilane,
Isobutyl triethoxy silane, trimethoxysilane, isobutyl group tripropoxy silane, three butoxy silane of isobutyl group,
T-butyltriethoxysilane, tertiary butyl tripropoxy silane, three butoxy silane of tertiary butyl, cyclohexyltriethyloxysilane,
Cyclohexyl tripropoxy silane, tetraethoxysilane, tetramethoxy-silicane, tetrapropoxysilane, four butoxy silanes etc..
The molar ratio of the organo-aluminum compound and the second external electron donor is calculated as 1 with aluminium/silicon or with aluminium/oxygen:1~60:
1, preferably 5:1~30:1.
The molar ratio of some embodiments according to the present invention, second external electron donor and the first external electron donor is
1-30, preferably 5-30.
In the method for the invention, preferably before the homopolymerization of second stage, make the second outer electron and the first rank
Catalytic component in section reaction product comes into full contact with.In some preferred embodiments, the second dispatch from foreign news agency daughter can be added
In the first stage on the feeding line after reactor before second stage reactor, or in the charging of second stage reactor
Pipe front end, the purpose is to carry out pre-contact with the catalyst in the reaction product of first stage first before second stage is reacted
Reaction.
For high fondant-strength impact polypropylene, due to being the material of heterogeneous structure, the factor for influencing melt strength just becomes
It obtains complex.With the method for the invention it is preferred to which the melt index of the Noblen obtained through the first step is obtained with second step
To the ratio between the melt index of polypropylene material comprising propylene homopolymer component and ethylene-butene-1 copolymer component be more than or
Equal to 0.6, and it is less than or equal to 1.It is also preferred that the weight ratio of first Noblen and the second Noblen is
40:60-60:40.It is further preferred that the ethylene-butene-1 copolymer component and the weight ratio of propylene homopolymer component are
11-80:100.By the way that the propylene homopolymer component of the impact polypropylene material of the present invention is set as including having different meltings
Index, and the combination of at least two Noblens with special ratios relationship, make the polypropylene material of the composition present invention
With specific dispersed phase, under being further combined of the dispersed phase and rubber phase, generating both has high melt strength, simultaneously
Impact polypropylene material with good rigidity and toughness.
, according to the invention it is preferred to which the propylene homopolymer component has following feature：Under 230 DEG C, the load of 2.16kg
The melt index of measurement is 0.1-15g/10min, preferably 0.1-6g/10min；Molecular weight distribution Mw/Mn=6-20；Molecular weight is big
It is greater than or equal to 1.5 weight % in the content of 5,000,000 fractions, and is less than or equal to 5 weight %；Molecular weight is less than 50,000 fractions
Content is greater than or equal to 15.0 weight %, and is less than or equal to 40 weight %；Mz+1/MnMore than or equal to 70, and it is less than 150.
In second step, it is 0.2- that the dosage of 1- butylene, which is preferably the ratio between 1- butylene and the total volume of 1- butylene and ethylene,
0.8.Preferably, in second step, the volume ratio of hydrogen and the total amount of 1- butylene and ethylene is 0.02-1.Meanwhile as described above,
In the first phase, the dosage of hydrogen for example can be 0-200ppm.In second stage, the dosage of hydrogen can be 2000-
20000ppm.In the present invention, have high fondant-strength to obtain, be provided simultaneously with the anti-impact poly- third of higher rigidity and toughness
The control of the composition of alkene material, dispersed phase and continuous phase, structure or performance is particularly significant.The present invention passes through these preferred conditions
The rubber phase of the molecular weight distribution, ethylene contents that are advantageously implemented the purpose of the present invention can be prepared, to be had
The impact polypropylene material of more preferable performance.
In a preferred embodiment of the invention, the yield of the first Noblen and the second Noblen is 40:60-
60:40.Ethylene-butene-1 copolymer component and the productivity ratio of propylene homopolymer component are 11-80:100.
The polymerisation of the first step can be in Liquid-liquid, or is carried out in gas phase-gas phase, or uses liquid-gas group
Conjunction technology carries out.When carrying out liquid phase polymerization, polymerization temperature is 0~150 DEG C, preferably 60~100 DEG C；Polymerization pressure should be higher than that
Saturated vapour pressure of the propylene under corresponding polymerization temperature.In gas-phase polymerization, polymerization temperature is 0~150 DEG C, with 60~100 DEG C
Preferably；Polymerization pressure can be normal pressure or higher, and preferably pressure is 1.0~3.0MPa (gauge pressure, similarly hereinafter).
The polymerisation of second step carries out in the gas phase.The gas-phase reactor can be gas-phase fluidized-bed, gas phase moving bed,
Or bubble agitation bed reactor.The temperature of polymerization is 0~150 DEG C, preferably 60~100 DEG C.Polymerization pressure is less than propylene point
Depress liquefied any pressure.
The reaction temperature of preferred embodiment according to the present invention, first stage is 50-100 DEG C, preferably 60-85 DEG C；The
The reaction temperature of two-stage is 55-100 DEG C, preferably 60-85 DEG C；The reaction temperature of second step is 55-100 DEG C, preferably 60-85
℃。
According to the method for the present invention, polymerisation can be carried out continuously, and can also intermittently be carried out.
According to the method for the present invention, the M of the room temperature trichloro-benzenes soluble matter of the polypropylene material obtained through second stepwWith room temperature
The M of trichlorine benzene insolublewThe ratio between be more than 0.5, and be less than 1, preferably greater than 0.5, and be less than 0.8；In ethylene-butene-1 copolymer
Butene content be greater than or equal to 20 weight %, and be less than or equal to 45 weight %.The rigidity of the polypropylene material so obtained
It is advanced optimized with toughness, while ensureing have higher melt strength.In the present invention, room temperature xylene soluble part
Content is measured according to ASTM D5492 the methods.Herein, it is readily appreciated that, it is so-called that " butylene in ethylene-butene-1 copolymer contains
Amount " can be understood as being copolymerized in the ethylene-butene-1 copolymer formed by vinyl monomer and 1- butene monomers, by butene monomers
The weight content of composition part.
According to the method for the present invention, what the polypropylene material obtained through second step measured under 230 DEG C, the load of 2.16kg
Melt index is 0.1-15g/10min, preferably 0.1-6g/10min；The molecular weight distribution M of the materialw/MnIt is less than or equal to
10, and it is greater than or equal to 4；Mz+1/MwMore than 10, and it is less than 20.
In a preferred embodiment of the invention, method of the invention further includes using α or β crystalline substance nucleating agents to made
Standby obtained impact polypropylene material is further modified, to further increase the rigidity or toughness of polyacrylic resin material.It is applicable in
α it is brilliant and β crystalline substances are nucleater modified, be known technology in the industry.The usual weight of nucleating agent and the ratio of polypropylene total weight are
(0.005~3):100.
The present invention also provides the impact polypropylene materials for the high fondant-strength that a kind of basis method as described above is prepared
Material, including propylene homopolymer component and ethylene-butene-1 copolymer component, wherein the propylene homopolymer component includes at least the
One Noblen and the second Noblen；Ethylene-butene-1 copolymer component and the weight ratio of propylene homopolymer component are
11-80:100, and the butene content in ethylene-butene-1 copolymer is greater than or equal to 20 weight %, and it is less than or equal to 45
Weight %.
The present invention uses ethylene -1- butylene-random copolymer as rubber components, also, the present inventor passes through
A large number of experiments is found, in the impact polypropylene material of the present invention, uses ethylene-butene-1 copolymer component and Noblen
The weight ratio of component is 11-80:100, effect is preferable；Further, when keeping the butene content in ethylene-butene-1 copolymer big
In or be equal to 20 weight %, and less than or equal to 45 weight % when, obtain rigidity and the preferable impact polypropylene material of toughness.This
The polypropylene product of invention has preferable rigid-tough balance.
The room temperature xylene soluble content of impact polypropylene material according to the present invention is preferably greater than 10 weight %, and small
In 30 weight %；The M of room temperature trichloro-benzenes soluble matterwWith the M of room temperature trichlorine benzene insolublewThe ratio between preferably greater than 0.5, and be less than 1,
Preferably greater than 0.5, it is less than 0.8.The rigidity and toughness of polypropylene material are advanced optimized, and higher melt is provided simultaneously with
Intensity.
The melt index range of the impact polypropylene material of the present invention is preferably controlled in 0.1-15g/10min, preferably 0.1-
10g/10min, further preferably 0.1-6.0g/10min.The melt index measures under 230 DEG C, the load of 2.16kg.For height
Melt strength impact polypropylene, due to being the material of heterogeneous structure, influencing the factor of melt strength just becomes complex.This hair
A person of good sense has found, in order to ensure the high fondant-strength of product, the molecular weight distribution M of the impact polypropylene materialw/MnPreferably smaller than
Or it is equal to 10, and it is greater than or equal to 4, Mz+1/MwMore than 10, and it is less than 20, preferably greater than 10, is less than 15.
In some preferred embodiments, the butene content of impact polypropylene material of the invention is 5-20 weight %.
Impact polypropylene material according to the present invention, molecular weight polydispersity index (PI) are 4-8, preferably 4.5-6.
According to impact polypropylene material provided by the invention, by carrying out propylene in the presence of the first Noblen
Homopolymerization obtains including the propylene homopolymer component of the first Noblen and the second Noblen, then in the propylene
Ethylene -1- butenes are carried out in the presence of homopolymer component, and the material comprising ethylene-butene-1 copolymer is obtained by the reaction to make
It is standby.It can be seen that the impact polypropylene material of the present invention is not propylene homopolymer component and ethylene-butene-1 copolymer component
Be simply mixed, but specific ethylene -1- butenes are further carried out on the basis of specific propylene homopolymer component
React the globality polypropylene material for including Noblen and ethylene-butene-1 copolymer obtained later.
The polypropylene material of the present invention also has preferable heat resistance, using the DSC final acrylic resins measured
Melting peak temperature TmMore than or equal to 158 DEG C.
In the preparation method of the impact polypropylene material of the present invention, the second external electron donor of addition can be with the first rank
Catalytic active center in section homopolymerization products material reacts, and generates new catalytic active center, continues to draw in second stage
Propylene polymerization is sent out into the homopolymer polymer with first stage products obtained therefrom mass difference great disparity.Second external electron donor is than first
External electron donor has higher hydrogen response, can prepare high fusion index polymer in the presence of a small amount of hydrogen.Cause
This, can by adjusting the external electron donor dosage of different phase, type when concatenated two reactor or intermittently operated is added with
And the addition of hydrogen, it is not required to use special catalyst, the present invention that can obtain containing big in the case of little hydrogen dosage
Measure super high molecular weight fraction, the homopolypropylene component of wider molecular weight distribution.Then by selecting suitable 1- butylene/(1-
Butylene+ethylene), hydrogen/(1- butylene+ethylene) and temperature and pressure, further sent out on the basis of homopolypropylene component
Raw ethylene -1- butenes reaction, the high fondant-strength for obtaining the rubber components with particular characteristic containing certain content are anti-
Rush polypropylene.The Nomenclature Composition and Structure of Complexes control of rubber phase component ensure that it has high fondant-strength, the certain content of rubber components
It is ensure that compared with high impact resistance, suitable molecular weight distribution also makes polymer have good processing performance in addition.Also
It is to say, the present invention selects the suitable of each homopolymerization and copolyreaction by the way that the multiple propylene homo stages of reaction are arranged
Each response parameter and reaction condition, to generate suitable continuous phase and rubber domain and combination thereof relationship,
The polypropylene material with excellent performance is obtained on the basis of this.
Impact polypropylene material provided by the invention is due to high melt strength, also having high rigidity and high tenacity special
Point, thus be the excellent material for being suitable for the fields such as automobile component, medical instrument, household items.High melt provided by the invention
The preparation method of intensity impact polypropylene material is simple and effective, easily operated.
Specific implementation mode
Below will by specific embodiment, the present invention is described further, but do not constitute to the present invention any limit
System.
The related data of polymer are obtained by following test method in embodiment：
1. polymer room temperature xylene soluble content (characterizing rubber-phase content) is according to ASTM D5492 the methods
It measures；
2. resin stretched intensity is measured by 1040.2 methods of GB/T；
3. melt mass flow rate (also known as melt index, MFR)：According to ASTM D1238 the methods, with CEAST public affairs
7026 type fusion index instruments are taken charge of, are measured under 230 DEG C, 2.16kg load；
4. bending modulus：It is measured according to 9341 the methods of GB/T；
5. simply supported beam notch impact strength：It is measured according to 1043.1 the methods of GB/T；
6. ethylene contents and butene content：Using nuclear magnetic resonance method determination.Using Bruker companies of Switzerland AVANCE
III 400MHz nuclear magnetic resonance chemical analysers (NMR), 10 millimeters of probes measure.Solvent is deuterated o-dichlorohenzene, and about 250mg samples are set
In 2.5ml deuterated solvents, homogeneous solution is formed in 140 DEG C of oil bath heating dissolved samples.Acquire 13C-NMR, probe temperature 125
DEG C, using 90 ° of pulses, sampling time AQ is 5 seconds, and delay time D1 is 10 seconds, scanning times 5000 times or more.Other operations,
The common NMR requirement of experiment of the execution such as spectral peak identification, bibliography include Eric T.Hsieh, and James C.Randall,
Ethylene-1-Butene Copolymers.1.Comonomer Sequence Distribution,
Macromolecules,15,353-360(1982)。
7. melt strength：Using the production of German Geottfert Werkstoff Pruefmaschinen companies
Rheotens melt strength instrument measures.Polymer is after single screw extrusion machine fusion plastification, then warp is equipped with 30/2 draw ratio mouth mold
90 ° steering the downward melt extrusion material strips of head, the material strip be clamped in one group of two roller with constant acceleration opposite direction rotating it
Between be uniaxially stretched, the power of melt drawn process is measured and recorded by the load cell being connected with draw roll, will be stretched to
The maximal force measured when melt fracture is defined as melt strength.
8. molecular weight polydispersity index (PI)：Resin sample is molded into the thin slice of 2mm at 200 DEG C, using the U.S.
ARES (advanced rheometer expansion system) rheometer of Rheometric Scientific Inc, under 190 DEG C and nitrogen protection
To sample carry out dynamic frequency scanning, select parallel plate fixtures, determine strain amplitude appropriate with ensure experiment linear zone into
Row, the storage modulus (G ') of determination sample, Loss modulus (G ") etc. with frequency variation.Molecular weight polydispersity index PI=105/
Gc, wherein Gc(unit：Pa it is) modulus value of G '-frequency curves and G "-frequency curve point of intersection.
9. molecular weight (Mw、Mn) and molecular weight distribution (Mw/Mn, Mz+1/Mw)：Using Britain Polymer
Laboratories companies produce 220 gel permeation chromatographs of PL-GPC or the GPCIR instrument of Polymer Char companies of Spain production
The molecular weight and molecular weight distribution of (IR5 concentration detectors) determination sample, chromatographic column are 3 series connection PLgel 13um Olexis
Column, solvent and mobile phase are 1,2,4- trichloro-benzenes (antioxidant 2 containing 250ppm, 6- dibutyl p-cresols), 150 DEG C of column temperature, stream
Fast 1.0ml/min carries out universal calibration using PL companies EasiCal PS-1 Narrow distribution polystyrene standard items.Wherein room temperature three
The preparation process of chlorobenzene soluble matter is as follows：Precise sample and trichlorine benzene solvent dissolve 5 hours at 150 DEG C, at 25 DEG C
Using quantitative glass filter paper filtering after standing 15 hours, the solution of room temperature trichloro-benzenes soluble matter is obtained for measuring.Using known
The polypropylene of concentration is corrected GPC area under the curves, determines the content of room temperature trichloro-benzenes soluble matter, room temperature trichlorine benzene insoluble
Molecular weight data be calculated using the GPC data and the GPC data of room temperature trichloro-benzenes soluble matter of raw sample.
Embodiment 1
Propylene polymerization carries out on polypropylene plant, and the capital equipment of the device includes prepolymerization reactor, the first ring
Pipe reactor, the second annular-pipe reactor and third gas-phase reactor.Polymerization and steps are as follows.
(1) prepolymerization
Major catalyst (DQC-401 catalyst, sinopec catalyst Co. Beijing Ao Da branch companies provide), co-catalyst
(triethyl aluminum), the first external electron donor (isopropyl cyclopentyl dimethoxysilane, IPCPMS) are through 6 DEG C, 20min pre-contact
Afterwards, it is added continuously and continuously stirs autoclave prepolymerization reactor progress pre-polymerization reactor.Into the triethyl aluminum of prepolymerization reactor
(TEA) flow is 6.33g/hr, and isopropyl cyclopentyl dimethoxysilane flow is 0.3g/hr, and major catalyst flow is 0.6g/
Hr, TEA/IPCPMS ratio are 50 (mol/mol).Prepolymerization carries out under propylene liquid-phase bulk environment, and temperature is 15 DEG C, when stop
Between be about 4min, pre-polymerization multiple of catalyst is about 80~120 times under the conditions of this.
(2) first step：Propylene homo closes reaction
First stage：Pre-polymerization rear catalyst is closed continuously into completion first stage propylene homo in the first annular-pipe reactor
Reaction, 70 DEG C of the polymeric reaction temperature of the first annular-pipe reactor, reaction pressure 4.0MPa；In the charging of first annular-pipe reactor not
Hydrogenation, the density of hydrogen ﹤ 10ppm of on-line chromatograph detection, obtains the first Noblen A.
Second stage：The isobutyl triethoxy silane of 0.63g/hr is added with the propylene of the second annular-pipe reactor
(IBTES) it is mixed with the reaction stream from the first annular-pipe reactor, TEA/IBTES ratios are 5 (mol/mol), and wherein IBTES is
For the second external electron donor.70 DEG C of the polymeric reaction temperature of second annular-pipe reactor, reaction pressure 4.0MPa；Also with propylene feed
A certain amount of hydrogen is added, density of hydrogen is 3300ppm in on-line chromatograph detection charging, and second is generated in the second annular-pipe reactor
Noblen B obtains the propylene homopolymer component for including the first Noblen and the second Noblen.
(3) second step：Second fourth copolymerization
A certain amount of hydrogen, H are added in third reactor2/(C2+C4)=0.06 (v/v), C4/(C2+C4(the v/ of)=0.45
v)(C2And C4Respectively refer to for ethylene and 1- butylene), it is total to continue initiation Ethylene/1-butene in third reactor for 75 DEG C of reaction temperature
Polymerisation generates ethylene-butene-1 copolymer component C.
Final product contains the first Noblen, the second Noblen and ethylene-butene-1 copolymer component, warp
The activity and heat drying of wet nitrogen removal unreacted catalyst, obtain polymer powders.It will be added in the obtained powder of polymerization
The calcium stearate of 168 additives of IRGAFOS of 0.1wt%, IRGANOX 1010 additive and 0.05wt% of 0.1wt% is used
Double screw extruder is granulated.Resulting polymers analysis result and polymer physics performance are listed in Tables 1 and 2.
Embodiment 2
Catalyst used in embodiment 2, pre- complexing, polymerization process condition and auxiliary formula and addition and embodiment 1
It is identical.Difference from Example 1 is：Amounts of hydrogen in second stage in second reactor becomes 7000ppm, second step gas
H in phase reaction device2/(C2+C4) it is adjusted to 0.20 (v/v).Resulting polymers analysis result and polymer physics performance are listed in 1 He of table
Table 2.
Embodiment 3
Catalyst used in embodiment 3, pre- complexing, polymerization process condition and auxiliary formula and addition and embodiment 1
It is identical.Difference from Example 1 is：Amounts of hydrogen in second stage in second reactor becomes 10000ppm, second step
H in gas-phase reactor2/(C2+C4) it is adjusted to 0.51 (v/v).Resulting polymers analysis result and polymer physics performance are listed in table 1
With table 2.
Embodiment 4
Catalyst used in embodiment 4, pre- complexing, polymerization process condition and auxiliary formula and addition and embodiment 1
It is identical.Difference from Example 1 is：Second external electron donor is changed to 2,-isopropyl -2- isopentyl -1,3- dimethoxys
Propane (IPPMP), addition is constant, and the amounts of hydrogen in second stage in second reactor is adjusted to 4000ppm.Resulting polymers point
Analysis result and polymer physics performance are listed in Tables 1 and 2.
Embodiment 5
Catalyst used in embodiment 5, pre- complexing, polymerization process condition and auxiliary formula and addition and embodiment 3
It is identical.Difference from Example 3 is：First external electron donor is changed to isopropyl -2- isobutyl groups-dimethoxysilane
(IPBMS), addition is constant.Resulting polymers analysis result and polymer physics performance are listed in Tables 1 and 2.
Embodiment 6
Catalyst used in embodiment 6, pre- complexing, polymerization process condition and auxiliary formula and addition and embodiment 1
It is identical.Difference from Example 1 is：Amounts of hydrogen in second stage in second reactor becomes 6000ppm, second step gas
H in phase reaction device2/(C2+C4) it is adjusted to 0.15 (v/v), C4/(C2+C4) it is adjusted to 0.25 (v/v).Resulting polymers analysis result and
Polymer physics performance is listed in Tables 1 and 2.
The result shown in the Tables 1 and 2, which can be seen that the polypropylene material being prepared according to the method for the present invention, to be had
Higher melt strength, while there is higher tensile strength, bending modulus, notch impact strength.Therefore, it carries through the invention
The method of confession can prepare the impact polypropylene material of high fondant-strength, high rigidity and high tenacity.It is this to have excellent performance
Polypropylene material is with a wide range of applications.
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 implementation modes 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 implementation mode
In, those can suitably be combined with other embodiment with reference to the embodiment of another embodiment, this is will be by this
Field technology personnel are 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 (12)
1. a kind of preparation method of high fondant-strength impact polypropylene material, including：
The first step：Propylene homo reacts, including：
First stage：Under the action of the Ziegler-Natta catalyst comprising the first external electron donor, in hydrogen presence or not
In the presence of carry out propylene homo reaction, obtain the reaction stream for including the first Noblen；
Second stage：The catalyst being added in the second external electron donor and the reaction stream carries out complex reaction, then the
Propylene homo reaction is carried out in the presence of one Noblen and hydrogen, generates the second Noblen, is obtained comprising the one the third
The propylene homopolymer component of polyamino alkenyl object and the second Noblen；
Wherein,
The melting that first Noblen and the propylene homopolymer component measure under 230 DEG C, the load of 2.16kg refers to
Number is respectively 0.001-0.4g/10min and 0.1-15g/10min；
Second step：Ethylene -1- butenes react, and are included in the presence of the propylene homopolymer component and hydrogen and carry out ethylene
With 1- butylene gas phase copolymerizations, ethylene-butene-1 copolymer component is generated, obtains including the propylene homopolymer component and second
The polypropylene material of alkene-butene-1 copolymer component；
The M of the room temperature trichloro-benzenes soluble matter of the polypropylene material obtained through second stepwWith the M of room temperature trichlorine benzene insolublewThe ratio between it is big
In or be equal to 0.64, and be less than 1；
Butene content in the ethylene-butene-1 copolymer component is more than 20 weight %, and is less than or equal to 45 weight %.
2. according to the method described in claim 1, it is characterized in that, it is R that first external electron donor, which is selected from general formula,1R2Si
(OR3)2At least one of compound；Wherein, R2With R1It is each independently selected from C1-C6Linear or branched alkyl group, C3-C8Ring
Alkyl and C5-C12Heteroaryl, R3For C1-C3Straight chain aliphatic.
3. according to the method described in claim 1, it is characterized in that, second external electron donor be selected from as chemical general formula (I),
(II) and at least one of (III) compound represented；
Wherein, R1And R2It is each independently selected from C1-C20One kind in straight chain, branched or cricoid aliphatic group, R3、R4、
R5、R6、R7And R8It is each independently selected from hydrogen atom, halogen atom, C1-C20Linear or branched alkyl group, C3-C20Naphthenic base, C6-
C20Aryl, C7-C20Alkaryl and C7-C20One kind in aralkyl；R9、R10And R11It is each independently C1-C3Linear aliphatic base
Group, R12For C1-C6Linear or branched alkyl group or C3-C8Naphthene group.
4. according to the method described in claim 1, it is characterized in that, second external electron donor and the first external electron donor
Molar ratio is 5-30.
5. according to the method described in claim 4, it is characterized in that, first external electron donor is selected from methyl-cyclopentyl-two
Methoxy silane, ethyI-cyclopentyl-dimethoxysilane, n-propyl-cyclopenta-dimethoxysilane, two (2- methyl fourths
Base)-dimethoxysilane, two (3- methyl butyls)-dimethoxysilanes, 2- methyl butyls -3- methyl butyls-dimethoxy silicon
Alkane, two (2,2- Dimethyl-propyls)-dimethoxysilanes, 2- methyl butyls -2,2- Dimethyl-propyls-dimethoxysilane,
3- methyl butyls -2,2- Dimethyl-propyls-dimethoxysilane, dimethyldimethoxysil,ne, dimethyl diethoxy silicon
Alkane, second, isobutyl dimethoxy silane, methylcyclohexyl dimethoxy silane, methyl-isobutyl dimethoxysilane, dicyclohexyl
Dimethoxysilane, methyl-isopropyl dimethoxysilane, isopropyl-cyclopenta dimethoxysilane, bicyclopentyl dimethoxy
Base silane, isopropyl-at least one of isobutyl group dimethoxysilane and diisopropyl dimethoxy silane；
Second external electron donor is selected from 2,2- diisobutyl -1,3- dimethoxy propanes, 2,2- phenyl -1,3- dimethoxys
Propane, 2,2- benzyl -1,3- dimethoxy propanes, 2- isopropyl -2- isopentyl -1,3- dimethoxy propanes, the bis- (rings of 2,2-
Own methyl) -1,3- dimethoxy propanes, 2- isopropyls -2-3,7- dimethyl octyls-dimethoxy propane, 2,2- isopropyls -1,3-
Dimethoxy propane, 2- isopropyl -2- cyclohexyl methyl -1,3- dimethoxy propanes, 2,2- diisobutyl -1,3- diethoxies third
Alkane, 2,2- diisobutyl -1,3- dipropoxies propane, 2- isopropyl -2- isopentyl -1,3- di ethyl propyl ethers, 2- isopropyls -
2- isopentyl -1,3- dipropoxies propane, bis- (the cyclohexyl methyl) -1,3- di ethyl propyl ethers of 2,2-, n-propyl triethoxysilicane
Alkane, isopro-pyltriethoxysilane, isobutyl triethoxy silane, trimethoxysilane, isobutyl group tripropoxy silicon
Alkane, three butoxy silane of isobutyl group, t-butyltriethoxysilane, tertiary butyl tripropoxy silane, three butoxy silicon of tertiary butyl
Alkane, cyclohexyltriethyloxysilane, cyclohexyl tripropoxy silane, tetraethoxysilane, tetramethoxy-silicane, tetrapropoxy-silicane
At least one of alkane and four butoxy silanes.
6. according to the method described in claim 1, it is characterized in that, the melting of the propylene homopolymer component obtained through the first step refers to
The melting for the polypropylene material comprising propylene homopolymer component and ethylene-butene-1 copolymer component that number is obtained with second step refers to
The ratio between number is greater than or equal to 0.6, and is less than or equal to 1.
7. according to the method described in claim 1, it is characterized in that, first Noblen and the second Noblen
Weight ratio is 40:60-60:40；The ethylene-butene-1 copolymer component and the weight ratio of propylene homopolymer component are 11-80:
100。
8. according to the method described in claim 1, it is characterized in that, the propylene homopolymer component has following feature：
The melt index measured under 230 DEG C, the load of 2.16kg is 0.1-15g/10min；
Molecular weight distribution Mw/Mn=6-20；
The content that molecular weight is more than 5,000,000 fractions is greater than or equal to 1.5 weight %, and is less than or equal to 5 weight %；
The content that molecular weight is less than 50,000 fractions is greater than or equal to 15.0 weight %, and is less than or equal to 40 weight %；
Mz+1/MnMore than or equal to 70, and it is less than 150.
9. according to the method described in claim 8, it is characterized in that, the propylene homopolymer component at 230 DEG C, the load of 2.16kg
The melt index measured under lotus is 0.1-6g/10min.
10. according to the method described in claim 1, it is characterized in that, in second step, 1- butylene and 1- butylene and ethylene it is total
The ratio between volume is 0.2-0.8；The ratio between hydrogen and the total volume of 1- butylene and ethylene are 0.02-1.
11. according to the method described in any one of claim 1-10, which is characterized in that the reaction temperature of first stage is
50-100℃；The reaction temperature of second stage is 55-100 DEG C；The reaction temperature of second step is 55-100 DEG C.
12. according to the method described in any one of claim 1-10, which is characterized in that the reaction temperature of first stage is
60-85℃；The reaction temperature of second stage is 60-85 DEG C；The reaction temperature of second step is 60-85 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410602299.8A CN105623075B (en) | 2014-10-31 | 2014-10-31 | A kind of preparation method of the impact polypropylene material of high fondant-strength |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410602299.8A CN105623075B (en) | 2014-10-31 | 2014-10-31 | A kind of preparation method of the impact polypropylene material of high fondant-strength |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105623075A CN105623075A (en) | 2016-06-01 |
| CN105623075B true CN105623075B (en) | 2018-10-16 |
Family
ID=56038448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410602299.8A Active CN105623075B (en) | 2014-10-31 | 2014-10-31 | A kind of preparation method of the impact polypropylene material of high fondant-strength |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105623075B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112745583B (en) * | 2019-10-30 | 2022-07-29 | 中国石油化工股份有限公司 | High-gloss impact-resistant polypropylene composition and preparation method thereof |
| CN112745581B (en) * | 2019-10-30 | 2022-07-26 | 中国石油化工股份有限公司 | High-fluidity high-crystallization impact-resistant polypropylene material and preparation method thereof |
| CN112745582B (en) * | 2019-10-30 | 2022-07-26 | 中国石油化工股份有限公司 | Ultrahigh impact polypropylene material and preparation method thereof |
| CN112745580B (en) * | 2019-10-30 | 2022-09-09 | 中国石油化工股份有限公司 | High-fluidity, high-impact-resistance and high-temperature-resistance polypropylene material as well as preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891850A (en) * | 2009-05-19 | 2010-11-24 | 中国科学院化学研究所 | Polypropylene composite and preparation method thereof |
| CN102134290A (en) * | 2010-01-22 | 2011-07-27 | 中国石油化工股份有限公司 | Polypropylene with high melt strength and product thereof |
-
2014
- 2014-10-31 CN CN201410602299.8A patent/CN105623075B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891850A (en) * | 2009-05-19 | 2010-11-24 | 中国科学院化学研究所 | Polypropylene composite and preparation method thereof |
| CN102134290A (en) * | 2010-01-22 | 2011-07-27 | 中国石油化工股份有限公司 | Polypropylene with high melt strength and product thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105623075A (en) | 2016-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105622819B (en) | A kind of preparation method of the impact polypropylene material of high fondant-strength | |
| EP1801155B1 (en) | Polypropylene composition comprising a propylene homopolymer component | |
| CN105623077B (en) | A kind of impact polypropylene material of high fondant-strength and preparation method thereof | |
| CN103788265B (en) | A kind of polyacrylic preparation method with high fondant-strength | |
| CN105623075B (en) | A kind of preparation method of the impact polypropylene material of high fondant-strength | |
| CN106280018B (en) | A kind of high fondant-strength impact polypropylene expanded material, preparation and its application | |
| CN102134291A (en) | Method for preparing polypropylene with high melt strength | |
| US10066034B2 (en) | High performance Ziegler-Natta catalyst systems, process for producing such MgCl2 based catalysts and use thereof | |
| US20170022305A1 (en) | High performance ziegler-natta catalyst systems, process for producing such supported catalysts and use thereof | |
| EA024017B1 (en) | Improved process for polymerising propylene | |
| US10273319B2 (en) | High performance Ziegler-Natta catalyst systems, processes for producing such catalyst systems, and use thereof | |
| CN106674722B (en) | A kind of polypropylene blow moulding film and preparation method thereof | |
| CN106674721A (en) | High-melt strength high-impact polypropylene foaming expanded beads and preparation method thereof | |
| CN105623076B (en) | A kind of impact polypropylene material of high fondant-strength | |
| CN107325394B (en) | Polypropylene composition and high-performance flame-retardant antistatic polypropylene pipe | |
| CN106674584A (en) | High-melt-strength impact-resistant polypropylene foamed beads and preparation method thereof | |
| CN106674749B (en) | A kind of polypropylene blow moulding film and preparation method thereof | |
| CN105623103B (en) | A kind of impact polypropylene material of high fondant-strength | |
| CN107325395B (en) | Polypropylene composition and flame-retardant antistatic pipe | |
| US11111322B2 (en) | Low density ethylene-based polymers for low speed extrusion coating operations | |
| CN107325411B (en) | Flame-retardant antistatic random copolymerization polypropylene composition and pipe | |
| CN106317609B (en) | A kind of high fondant-strength impact polypropylene foaming plate and preparation method thereof | |
| CN106674719A (en) | Polypropylene blowing film and preparation method thereof | |
| JP6180517B2 (en) | Free radical process for making ethylene-based polymers using alkylated phenols | |
| DE112007003019T5 (en) | Propylene block copolymer |
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 |