CN105623103B - A kind of impact polypropylene material of high fondant-strength - Google Patents
A kind of impact polypropylene material of high fondant-strength Download PDFInfo
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Abstract
The invention provides a kind of impact polypropylene material of high fondant-strength, the polypropylene material includes atactic copolymerized polypropene continuous phase and propylene ethylene copolymers rubber domain；The room temperature xylene soluble content of the material is more than or equal to 10 weight %, and is less than or equal to 35 weight %；And the ratio between the Mw of the room temperature trichloro-benzenes DDGS of the material and Mw of room temperature trichlorine benzene insoluble is more than 0.4, less than or equal to 1.There is high melt strength according to polypropylene material provided by the invention, the characteristics of heat-sealing also with high rigidity and high tenacity and easily, be widely used, such as suitable for fields such as automobile component, medicine equipment, household articles.
Description
Technical field
The present invention relates to a kind of polypropylene material, and in particular to the impact polypropylene material and its system of a kind of high fondant-strength
Preparation Method.
Background technology
Impact polypropylene have excellent high/low temperature impact strength, higher tensile strength, bending modulus etc. rigidity with
And higher heat resisting temperature, had been widely used in many fields, such as molding or the automobile component of extrusion molding, appliances parts, appearance
Device and household articles etc..Impact polypropylene is generally used for injection processing because its melt strength is relatively low, and is used for blow molding
When, the problems such as mold base size is unstable, and products thickness is uneven or even can not be molded be present.
The conventional way for improving melt strength of polypropylene is to reduce melt index, improve polypropylene molecule amount, but this
Material molten and extrusion can be brought difficult.Still an alternative is that widen molecular weight distribution, such as US7365136 and US6875826
A kind of method for preparing wide molecular weight distribution, high fondant-strength homopolymerization and atactic copolymerized polypropene is reported, it selects alkoxy
Silane is external electron donor (such as dicyclopentyl dimethoxyl silane), dense by adjusting hydrogen in the reactor of multiple series connection
Degree, come regulatory molecule amount size and distribution, realize 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 atactic copolymerized polypropene, it is by adjusting hydrogen in different reactor
Concentration prepare the high melt strength, propylene of wide molecular weight distribution or bimodal distribution, the property of catalyst is in each reactor
Do not adjust, thus preparation process needs a large amount of hydrogen.
CN102134290 and CN102134291 discloses a kind of wide molecular weight distribution, high fondant-strength HOPP
Preparation method, its use multiple tandem reactors by control external electron donor component the differential responses stage species and ratio
Example, in conjunction with the control of molecular weight regulator hydrogen usage, be prepared for wide molecular weight distribution, high fondant-strength HOPP or
Atactic copolymerized polypropene.
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 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 HOPP or atactic copolymerized polypropene.
Above-mentioned patent report be high fondant-strength HOPP or atactic copolymerized polypropene preparation method, that is,
Say, although the HOPP or atactic copolymerized polypropene that are prepared by these methods possess higher melt strength,
It is rigidity, toughness or erosion-resisting characteristics deficiency, so as to limit resulting polyacrylic application.Therefore it provides there is rubber group
Point and the impact polypropylene and preparation method thereof of the high fondant-strength of rubber disperse phase structure, high rigidity and toughness will have weight
Big meaning.
The content of the invention
The present inventor is by further investigation, there is provided a kind of high fondant-strength impact polypropylene material, this poly- third
Alkene material also has high tenacity, easily seals feature simultaneously.The polypropylene material applies to automobile component, medicine equipment, household
The excellent material in the fields such as articles for use.
Present invention also offers a kind of method for the impact polypropylene material for preparing high fondant-strength.Pass through the side of the present invention
The polypropylene material that method obtains also has the characteristics of high tenacity.
According to the present invention, there is provided a kind of impact polypropylene material of high fondant-strength, including atactic copolymerized polypropene connect
Continuous phase and propylene-ethylene copolymers rubber domain, wherein the atactic copolymerized polypropene continuous phase is random including at least first
COPP and the second atactic copolymerized polypropene, and first atactic copolymerized polypropene and the second atactic copolymerized polypropene
It is each independently selected from Propylene-ethylene random copolymer or propylene -1- butene random copolymers or ethylene-propylene -1- butylene three
Membered copolymer；The room temperature xylene soluble content of the material is more than or equal to 10 weight %, and is less than or equal to 35 weights
Measure %；And the ratio between the Mw (weight average molecular weight) of the room temperature trichloro-benzenes DDGS of the material and Mw of room temperature trichlorine benzene insoluble
More than 0.4, less than or equal to 1,0.4 is greater than, and less than or equal to 0.8.The polypropylene material have excellent rigidity and
Toughness, it is provided simultaneously with higher melt strength.
In the present invention, the content of rubber phase can be surveyed in terms of room temperature xylene soluble content according to CRYSTEX methods
It is fixed.Convenient to characterize, the molecular weight of rubber phase is with the Molecular weights of trichloro-benzenes DDGS.
In polypropylene material provided by the invention, atactic copolymerized polypropene provides as continuous phase for polypropylene material
Certain rigidity, propylene-ethylene copolymers rubber is as dispersed phase, it is possible to increase the toughness of polypropylene material.In order to ensure this
The product of invention has preferable rigid-tough balance, and the present invention uses ethylene-propylene copolymer as rubber components, also, this
The inventor of invention has found by lot of experiments, in the impact polypropylene material of the present invention, when the room temperature two for making the material
Ethylene contents in xylene solubles are more than or equal to 28 weight %, and when being less than 45 weight %, impact polypropylene material has
Preferable rigidity and toughness.Especially, in the present invention, by being arranged to atactic copolymerized polypropene continuous phase to comprise at least the
One atactic copolymerized polypropene and the second atactic copolymerized polypropene, and first atactic copolymerized polypropene and the second random copolymerization
Polypropylene is each independently selected from Propylene-ethylene random copolymer or propylene -1- butene random copolymers or ethylene-propylene -1-
Butene terpolymers, so that continuous phase and dispersed phase preferably mutually compound, produce the anti-of high fondant-strength and high tenacity
Rush polypropylene material.Herein, it is readily appreciated that, so-called " ethylene contents " can be understood as in the polymer that vinyl monomer participates in,
The weight content for the part being made up of vinyl monomer.Other " butene contents " of expression in the polymer, its meaning are similar.
In order to obtain higher melt strength, the melt index scope of impact polypropylene material of the invention is preferably controlled in
0.1-15g/10min, further preferably 0.1-6.0g/10min.The melt index determines under 230 DEG C, 2.16kg load.It is right
In high fondant-strength impact polypropylene, due to being the material of heterogeneous structure, influenceing the factor of melt strength just becomes complex.
The inventors discovered that in order to ensure the high fondant-strength of product, the molecular weight distribution mw/mn (weight of the impact polypropylene material
Average molecular weight/number-average molecular weight) 10 are preferably lower than or equal to, and more than or equal to 4, for example, 4,5,6,7,8,9 or 10；Mz+
1/Mw is preferably greater than or equal to 10, and preferably smaller than 20.
In some preferred embodiments, the ethylene contents of impact polypropylene material of the invention are 8-20 weight %；
And/or butene content is 0-10 weight %.
According to the impact polypropylene material of the present invention, molecular weight polydispersity index (PI) is 4-10, preferably 4.5-6.
In a preferred embodiment of the invention, the melt index of first atactic copolymerized polypropene is less than described second
The melt index of atactic copolymerized polypropene.
In a preferred embodiment of the invention, the first atactic copolymerized polypropene determines under 230 DEG C, 2.16kg load
Melt index be 0.001-0.4g/10min；Atactic copolymerized polypropene including the first atactic copolymerized polypropene at 230 DEG C,
The melt index determined under 2.16kg load is 0.1-15g/10min.It is preferred that 0.1-6 g/10min.
Preferably, the weight ratio of first atactic copolymerized polypropene and the second atactic copolymerized polypropene is 40:60-60:
40.By the way that the atactic copolymerized polypropene continuous phase of the impact polypropylene material of the present invention is arranged to include that there are different meltings to refer to
Number, and the combination of at least two atactic copolymerized polypropenes with special ratios relation, especially in the first random copolymerization poly- third
Alkene and atactic copolymerized polypropene including the first atactic copolymerized polypropene and the second atactic copolymerized polypropene have specific respectively
Under conditions of different molecular weight and molecualr weight distributions, make the polypropylene material of the composition present invention there is specific continuous phase,
The continuous phase is under being further combined of rubber phase with specific dispersed phase, and generation both has high melt strength, has simultaneously
Good rigidity and the impact polypropylene material of toughness.
According to the preferred embodiments of the invention, the atactic copolymerized polypropene for forming the impact polypropylene material of the present invention connects
It is continuous that mutually there is following feature：
The melt index determined under 230 DEG C, 2.16kg load is 0.1-10g/10min, preferably 0.1-6g/10min；
Molecular weight distribution mw/mn=6-20, preferably Mw/Mn=10-16；
The content that molecular weight is more than 5,000,000 fractions is more 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 more than or equal to 15.0 weight %, and is less than or equal to 40 weight %；
Mz+1/Mn is more than or equal to 70, and preferably smaller than 150.
, according to the invention it is preferred to ethylene contents are 0~6 weight % in atactic copolymerized polypropene continuous phase；And/or butylene
Content is 0~10 weight %.
According to impact polypropylene material provided by the invention, it in the presence of the first atactic copolymerized polypropene by carrying out
The random copolymerization of acrylic reacts to obtain the random copolymerization comprising the first atactic copolymerized polypropene and the second atactic copolymerized polypropene
Polypropylene continuous phase, propylene-ethylene copolyreaction is then carried out in the presence of the atactic copolymerized polypropene continuous phase and is obtained
It is prepared by material comprising propylene-ethylene copolymers rubber phase.As can be seen here, impact polypropylene material of the invention is not nothing
Rule COPP continuous phase is simply mixed with propylene-ethylene copolymers rubber domain, but in atactic copolymerized polypropene
Further carry out obtaining after propylene-ethylene copolyreaction on the basis of continuous phase comprising atactic copolymerized polypropene continuous phase and
The globality polypropylene material of propylene-ethylene copolymers rubber domain.
According to the preferred embodiments of the invention, atactic copolymerized polypropene continuous phase includes the nothing with what second step obtained
Rule COPP continuous phase and the ratio between the melt index of polypropylene material of propylene-ethylene copolymers rubber domain be more than or
Equal to 0.6, less than 1.
According to the preferred embodiments of the invention, propylene-ethylene copolymers rubber domain connects with atactic copolymerized polypropene
The weight ratio of continuous phase is 11-80:100.
The polypropylene material of the present invention also has preferable heat resistance and preferable heat sealability, using DSC measure
The melting peak temperature T of final acrylic resinmMore than or equal to 145 DEG C, less than or equal to 158 DEG C.
According to the present invention, a kind of method for preparing high fondant-strength impact polypropylene material as described above is additionally provided,
Including：
The first step：The random copolymerization reaction of acrylic, including：
First stage：In the presence of the Ziegler-Natta catalyst comprising the first external electron donor, exist in hydrogen
The random copolymerization that propylene and ethene and/or 1- butylene are carried out in the absence of or is reacted, and obtains including the first atactic copolymerized polypropene
Reaction stream；
Second stage：Add the second external electron donor and carry out complex reaction with the catalyst in the reaction stream, then
The random copolymerization that propylene and ethene and/or 1- butylene are carried out in the presence of the first atactic copolymerized polypropene and hydrogen is reacted, production
Raw second atactic copolymerized polypropene, obtain the random copolymerization comprising the first atactic copolymerized polypropene and the second atactic copolymerized polypropene
Polypropylene continuous phase；
Wherein,
First atactic copolymerized polypropene and comprising the first atactic copolymerized polypropene and the second atactic copolymerized polypropene
The melt index that atactic copolymerized polypropene continuous phase determines under 230 DEG C, 2.16kg load is respectively 0.001-0.4g/
10min and 0.1-15g/10min；
Second step：Propylene-ethylene copolyreaction, carried out in the presence of the atactic copolymerized polypropene continuous phase and hydrogen
Propylene-ethylene gas phase copolymerization, propylene-ethylene copolymers rubber domain is produced, obtains including the random copolymerization poly- third
The material of alkene continuous phase and propylene-ethylene copolymers rubber domain.
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 is preferably carried out in the reactor of two or more serial operations.
The method according to the invention is the method for the direct catalytic polymerization of Ziegler-Natta catalyst.By using going here and there
Two or more different types of external electron donors are used respectively in multiple reactors of connection, select suitable external electron donor to use
Measure, composition of the dosage of different chain-transferring agent hydrogen, reaction monomers etc. in association reaction, preparation has particular melt index
, the atactic copolymerized polypropene continuous phase of extremely wide molecular weight distribution containing a large amount of super high molecular weight components, and on this basis
The combined polymerization of propylene and ethene is further carried out, obtains being scattered in the rubber phase in continuous phase, then by controlling copolyreaction
Reaction condition controls the composition of rubber phase, structure and content etc., obtains the impact polypropylene material with high fondant-strength effect
Material.
In method provided by the invention, used catalyst is Ziegler-Natta catalyst, preferably with Gao Li
The catalyst of structure selectivity.The Ziegler-Natta catalyst of high stereoselective described herein refers to 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, its 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 Ziegler-Natta catalyst used in the method for the present invention (can claim again
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.
The preferred alkyl aluminum chemical combination of organo-aluminum compound in the Ziegler-Natta catalyst used in the method for the present invention
In thing, 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 mol 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 formula,1R2Si(OR3)2Compound in extremely
Few one kind；Wherein, R2With R1It is each independently selected from C1-C6Straight or branched alkyl, C3-C8Cycloalkyl and C5-C12Heteroaryl,
R3For C1-C3Straight chain aliphatic.Instantiation includes but are not limited to dicyclopentyl dimethoxyl silane, isopropyl cyclopentyl
Dimethoxysilane, isopropyl butyldimethoxysilane, bipyridyl dimethoxysilane, diisopropyl dimethoxy silicon
Alkane etc..
The mol ratio of the organo-aluminum compound and the first external electron donor is calculated as 1 with aluminium/silicon:1~100:1, be preferably
10:1~60:1.
In the method according to the invention, the catalyst comprising the first external electron donor can be added directly into the first step without
Advise in copolymerization reactor, the known pre-contact of industry and/or prepolymerization can also be passed through and then be added to the first step being randomly total to
In poly- reactor.The prepolymerization refers to that catalyst carries out the prepolymerization of certain multiplying power at a lower temperature, to obtain preferably
Particle shape and dynamic behavior control.The prepolymerization can be the continuous prepolymerization of liquid-phase bulk, can also be molten in inertia
Batch pre-polymerization in the presence of agent.Prepolymerization temperature is usually -10~50 DEG C, preferably 5~30 DEG C.Before prepolymerization technology
Pre-contacting steps is optionally set.The pre-contacting steps refers to co-catalyst in catalyst system, external electron donor and master
Catalyst (solid active center component) carries out the complex reaction of catalyst system, to obtain the caltalyst with polymerization activity
System.The generally control of the temperature of pre-contacting steps 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 thing；
Wherein R1And R2It is each independently selected from C1-C20One kind in straight chain, branched or ring-type aliphatic group, R3、
R4、R5、R6、R7And R8It is each independently selected from hydrogen atom, halogen atom, C1-C20Straight or branched alkyl, C3-C20Cycloalkyl,
C6-C20Aryl, C7-C20Alkaryl and C7-C20One kind in aralkyl, and R3、R4、R5、R6、R7And R8In any two between
Optionally key is linked to be ring；R9、R10And R11It is each independently C1-C3Straight chain aliphatic, R12For C1-C6Straight or branched alkyl
Or C3-C8Naphthene group.The instantiation of second external electron donor includes but are not limited to 2,2- diisobutyl -1,3- dimethoxies
Base propane, 2,2- phenyl -1,3- dimethoxy propanes, 2,2- benzyl -1,3- dimethoxy propanes, 2- isopropyl -2- isoamyls
Double (the cyclohexyl methyl) -1,3- dimethoxy propanes of base -1,3- dimethoxy propanes, 2,2-, 2- isopropyl -2-3,7- diformazans are pungent
Base-dimethoxy propane, 2,2- isopropyl -1,3- dimethoxy propanes, 2- isopropyl -2- cyclohexyl methyl -1,3- dimethoxys
Propane, 2,2- diisobutyl -1,3- di ethyl propyl ethers, 2,2- diisobutyl -1,3- dipropoxies propane, 2- isopropyls -2-
Isopentyl -1,3- di ethyl propyl ethers, 2- isopropyl -2- isopentyl -1,3- dipropoxies propane, 2,2- double (cyclohexyl methyls) -
1,3- di ethyl propyl ether, trimethoxysilane, isobutyl triethoxy silane, isopro-pyltriethoxysilane, four
Ethoxysilane silane etc..
The mol 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.
According to some embodiments of the present invention, the mol ratio of second external electron donor and the first external electron donor is
1-30, also preferably 5-30.
In the method for the invention, preferably the second outer electron and the are made before the random copolymerization reaction of second stage
Catalytic component in one stage reaction product fully contacts.In some preferred embodiments, the second dispatch from foreign news agency daughter can be with
Add in the first stage on the feeding line after reactor before second stage reactor, or in second stage reactor
Feed pipe front end, carried out the purpose is to the catalyst in the reaction product before second stage is reacted first with the first stage pre-
Haptoreaction.
Preferably, in second step, the dosage of ethene accounts for the 20-60% of the cumulative volume of ethene and propylene for ethene.
In two steps, the volume ratio of hydrogen and ethene and the total amount of propylene is 0.02-1.Meanwhile as described above, in the first phase, hydrogen
Dosage for example can be 0-200ppm.In second stage, the dosage of hydrogen can be 2000-20000ppm.In the present invention
In, possess high fondant-strength to obtain, be provided simultaneously with the impact polypropylene material of higher rigidity and toughness, dispersed phase and company
The control of the composition of continuous phase, structure or performance is particularly significant.The present invention can be prepared with favourable by these preferable conditions
In the ethylene contents for realizing the molecular weight distribution of the purpose of the present invention, rubber phase, gather so as to obtain the anti-impact with more preferable performance
Propylene material.
In a preferred embodiment of the invention, the yield of the first atactic copolymerized polypropene and the second atactic copolymerized polypropene
For 40:60-60:40.The productivity ratio of propylene-ethylene copolymers rubber domain and atactic copolymerized polypropene continuous phase is 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 is carried 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 is carried 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.
According to the preferred embodiments of the invention, the reaction temperature of 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
℃。
In a preferred embodiment of the invention, method of the invention also includes using α or β crystalline substance nucleators to made
Standby obtained impact polypropylene material is further modified, to improve the rigidity of polyacrylic resin material or toughness.Applicable α it is brilliant and
β crystalline substances are nucleater modified, are known technologies in the industry.The weight of usual nucleator and the ratio of polypropylene gross weight for (0.005~
3):100。
The method according to the invention, polymerisation can be carried out continuously, and can also intermittently be carried out.
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
Section propylene reacts with the catalytic active center in the copolymerization product material of ethene and/or butylene, generates new catalytic activity
Center, second stage continue to trigger propylene and ethene and/or butene polymerization into first stage products obtained therefrom mass difference
The random copolymerization polymer of great disparity.Second external electron donor has higher hydrogen response, Ke Yi than the first external electron donor
In the presence of a small amount of hydrogen, high fusion index polymer is prepared.Then by control the reaction condition of second step polymerisation come
The molecular weight of resulting polymers is controlled, this step is extremely important, the hydrogen response added using second stage in the first step
The second good external electron donor, under specific density of hydrogen, obtains the rubber phase molecule amount to match with continuous phase, so as to obtain
There must be the polypropylene material of superperformance, this is one of outstanding advantages of the present invention.The Nomenclature Composition and Structure of Complexes control of rubber phase component
System ensure that it possesses high fondant-strength, and the certain contents of rubber components ensure that it compared with high impact resistance, in addition suitably
Molecular weight distribution also causes polymer to have good processing characteristics.That is, the present invention is by setting multiple propylene randoms to be total to
The poly- stage of reaction prepares continuous phase, and selects suitable each response parameter of continuous phase and rubber domain preparation process and anti-
Condition is answered, to regulate and control the structure of caused continuous phase and rubber domain and performance and combinations thereof relation, in this base
The polypropylene material with premium properties is obtained on plinth.
Impact polypropylene material provided by the invention due to high melt strength, also with high rigidity and high tenacity and
The characteristics of easily sealing, thus apply to the excellent material in the fields such as automobile component, medicine equipment, household articles.The present invention carries
The preparation method of the high fondant-strength impact polypropylene material of confession is easy and effective, easily operated.
Embodiment
Below will by specific embodiment, the present invention is described further, but do not form to the present invention any limit
System.
The relevant data of polymer are obtained by following test method in embodiment：
1. the ethylene contents in room temperature xylene soluble content and room temperature xylene soluble part (characterize rubber-phase content
And the ethylene contents of rubber phase), determined using CRYSTEX methods, using the production of Polymer Char companies of Spain
CRYST-EX instruments (CRYST-EX EQUIPMENT, IR4+Detector), from a series of room temperature xylene soluble contents not
Same sample is corrected as standard specimen, and the room temperature xylene soluble content of standard specimen is determined using ASTM D5492.Instrument is certainly
Body institute band infrared detector can test propylene weight content in DDGS, contain for characterizing the ethene in room temperature xylene soluble part
Measure (ethylene contents in rubber phase)=100%- propylene weight contents.
2. resin stretched intensity is measured by the methods of GB/T 1040.2.
3. melt mass flow rate (also known as melt index, MFR)：It is public with CEAST according to ASTM D1238 methods describeds
7026 type fusion index instruments are taken charge of, are determined under 230 DEG C, 2.16kg load.
4. bending modulus：Determined according to the methods describeds of GB/T 9341.
5. simply supported beam notch impact strength：Determined according to the methods describeds of GB/T 1043.1.
6. ethylene contents：Determined using infrared spectrum (IR) method, demarcated using the standard specimen of nuclear magnetic resonance method determination.It is described
Magnetic nuclear resonance method uses 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 placed in 2.5ml deuterated solvents, in 140 DEG C of oil bath heating dissolving examinations
Sample forms homogeneous solution.13C-NMR is gathered, 125 DEG C of probe temperature, using 90 ° of pulses, sampling time AQ is 5 seconds, time delay
D1 is 10 seconds, scanning times more than 5000 times.The conventional NMR requirement of experiment of the execution such as other operation, spectral peak identifications.
7. butene content：Determined using infrared spectrum (IR) method, demarcated using the standard specimen of nuclear magnetic resonance method determination.It is described
Magnetic nuclear resonance method uses 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 placed in 2.5ml deuterated solvents, in 140 DEG C of oil bath heating dissolving examinations
Sample forms homogeneous solution.13C-NMR is gathered, 125 DEG C of probe temperature, using 90 ° of pulses, sampling time AQ is 5 seconds, time delay
D1 is 10 seconds, scanning times more than 5000 times.The conventional NMR requirement of experiment of the execution such as other operation, spectral peak identifications.Bibliography
Including Eric T.Hsieh, and James C.Randall, Ethylene-1-Butene Copolymers.1.Comonomer
Sequence Distribution,Macromolecules,15,353-360(1982)。
8. melt strength：Using the production of German Geottfert Werkstoff Pruefmaschinen companies
Rheotens melt strength instrument.Polymer is after single screw extrusion machine fusion plastification, then warp is equipped with 90 ° of 30/2 draw ratio mouth mold
The downward melt extrusion material strip of head is turned to, the material strip is carried out between being clamped in one group of two roller with constant acceleration opposite direction rotating
Uniaxial tension, measured by the load cell being connected with draw roll and record the power of melt drawn process, melt will be stretched to and broken
The maximal force measured when splitting is defined as melt strength.
9. molecular weight polydispersity index (PI)：Resin sample is molded into 2 mm thin slice at 200 DEG C, using the U.S.
Rheometric Scientific Inc ARES (advanced rheometer extension system) rheometer, under 190 DEG C and nitrogen protection
Dynamic frequency scanning is carried out to sample, from parallel plate fixtures, it is determined that appropriate strain amplitude is to ensure that experiment is entered in linear zone
OK, the storage modulus (G ') of determination sample, Loss modulus (G ") etc. with frequency change.Molecular weight polydispersity index PI=105/
Gc, wherein Gc(unit：Pa it is) G '-frequency curve and the modulus value of G "-frequency curve point of intersection.
10. molecular weight (Mw、Mn) and molecular weight distribution (Mw/Mn, Mz+1/Mw)：Using Britain Polymer Laboratories
Company produces the gel permeation chromatographs of PL-GPC 220 or GPCIR instrument (the IR5 Concentration Testings of Polymer Char companies of Spain production
Device) determination sample molecular weight and molecular weight distribution, chromatographic column is 3 series connection PLgel 13um Olexis posts, solvent and flowings
It is mutually 1,2,4- trichloro-benzenes (antioxidant 2 containing 250ppm, 6- dibutyl p-cresols), 150 DEG C of column temperature, flow velocity 1.0ml/min, adopts
Universal calibration is carried out with PL companies EasiCal PS-1 Narrow distribution polystyrenes standard items.The wherein system of room temperature trichloro-benzenes DDGS
Standby process is as follows：Precise sample and trichlorine benzene solvent, dissolve 5 hours at 150 DEG C, adopted after standing 15 hours at 25 DEG C
Filtered with quantitative glass filter paper, the solution for obtaining room temperature trichloro-benzenes DDGS is used to determine.Using the polypropylene pair of concentration known
GPC area under the curves are corrected, and determine the content of room temperature trichloro-benzenes DDGS, and the molecular weight data of room temperature trichlorine benzene insoluble is adopted
It is calculated with the GPC data of raw sample and the GPC data of room temperature trichloro-benzenes DDGS.
Embodiment 1
Propylene polymerization is carried 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 the 3rd Gas-phase reactor.Polymerization and step 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 (diisopropyl dimethoxy silane, DIPMS) are after 6 DEG C, 20min pre-contact, continuously
Ground, which adds, continuously stirs autoclave prepolymerization reactor progress pre-polymerization reactor.Triethyl aluminum (TEA) into prepolymerization reactor flows
It is 0.3g/hr to measure as 6.33g/hr, diisopropyl dimethoxy silane flow, and major catalyst flow is 0.6g/hr, TEA/
DIPMS ratios are 50 (mol/mol).Prepolymerization is carried out under propylene liquid-phase bulk environment, and temperature is 15 DEG C, and the residence time is about
4min, pre-polymerization multiple of catalyst is about 80~120 times under the conditions of this.
(2) first step：Propylene and ethylene random copolymerization
First stage：Pre-polymerization rear catalyst is continuously into completion first stage propylene in the first annular-pipe reactor and on a small quantity
Ethylene random copolymerization, wherein the ethene addition of the first endless tube is 10000ppm.First annular-pipe reactor polymerisation
Temperature 70 C, reaction pressure 4.0MPa；Not hydrogenation in the charging of first annular-pipe reactor, the density of hydrogen of on-line chromatograph detection
﹤ 10ppm, obtain the first atactic copolymerized polypropene A.
Second stage：0.63g/hr 2,2- bis- is added in the second annular-pipe reactor connected with the first annular-pipe reactor
Isobutyl group -1,3- dimethoxy propane (DIBMP) mixes with the reaction stream from the first annular-pipe reactor, TEA/DIBMP ratios
For 5 (mol/mol), wherein DIBMP is the second external electron donor.70 DEG C of the polymeric reaction temperature of second annular-pipe reactor, instead
Answer pressure 4.0MPa；A certain amount of hydrogen is additionally added with propylene feed, density of hydrogen is 1000ppm in on-line chromatograph detection charging,
The second atactic copolymerized polypropene B is produced in the second annular-pipe reactor, obtains including the first atactic copolymerized polypropene and the second nothing
Advise the atactic copolymerized polypropene continuous phase of COPP.
(3) second step：Propylene polymerization closes reaction
A certain amount of hydrogen, H are added in the 3rd reactor2/(C2+C3)=0.06 (v/v), C2/(C2+C3)=0.4 (v/v)
(C2And C3Ethene and propylene are referred to respectively), continue to trigger ethylene/propylene copolymer to close reaction, reaction temperature 75 in the 3rd reactor
DEG C, produce propylene-ethylene copolymers rubber domain C.
Final product contains the first atactic copolymerized polypropene, the second atactic copolymerized polypropene and propylene-ethylene copolymers
Rubber domain, the activity and heat drying of unreacted catalyst are removed through wet nitrogen, obtains polymer powders.Polymerization is obtained
Powder in add 0.1wt% additives of IRGAFOS 168,0.1wt% IRGANOX1010 additives and 0.05wt%
Calcium stearate, it is granulated with double screw extruder.Resulting polymers analysis result and polymer physics performance are listed in Tables 1 and 2.
Embodiment 2
Catalyst, pre- complexing, polymerization process condition and auxiliary formula and addition and embodiment 1 used in embodiment 2
It is identical.Difference from Example 1 is：The comonomer ethylene of first stage and second stage in the first step are changed to 1- fourths
Alkene, the addition of the first and second endless tubes is 10mol%.Resulting polymers analysis result and polymer physics performance are listed in table
1 and table 2.
Embodiment 3
Catalyst, pre- complexing, polymerization process condition and auxiliary formula and addition and embodiment 1 used in embodiment 3
It is identical.Difference from Example 1 is：The comonomer ethylene of first stage and second stage in the first step are changed to ethene
+ 1- butylene, the ethene addition of the first and second endless tubes is 6000ppm, and 1- butylene additions are 5mol%..Gained gathers
Compound analysis result and polymer physics performance are listed in Tables 1 and 2.
Embodiment 4
Catalyst, pre- complexing, polymerization process condition and auxiliary formula and addition and embodiment 1 used in embodiment 4
It is identical.Difference from Example 1 is：The comonomer ethylene addition of first stage and second stage in the first step change
For 30000ppm..Resulting polymers analysis result and polymer physics performance are listed in Tables 1 and 2.
Embodiment 5
Catalyst, pre- complexing, polymerization process condition and auxiliary formula and addition and embodiment 1 used in embodiment 5
It is identical.Difference from Example 1 is：Amounts of hydrogen in second stage in second reactor is changed into 10000ppm, second step
H in Gas-phase reactor2/(C2+C3) it is adjusted to 0.35 (v/v), C2/(C2+C3) it is adjusted to 0.3 (v/v).Resulting polymers analysis result and
Polymer physics performance is listed in Tables 1 and 2.
Embodiment 6
Catalyst, pre- complexing, polymerization process condition and auxiliary formula and addition and embodiment 1 used in embodiment 5
It is identical.Difference from Example 1 is：Amounts of hydrogen in second stage in second reactor is changed into 15000ppm, second step
H in Gas-phase reactor2/(C2+C3) it is adjusted to 0.6 (v/v), C2/(C2+C3) it is adjusted to 0.2 (v/v).Resulting polymers analysis result and
Polymer physics performance is listed in Tables 1 and 2.
Can be seen that the polypropylene material that the method according to the invention is prepared from the result shown in Tables 1 and 2 has
Higher melt strength, while there is higher tensile strength, bending modulus and notch impact strength.Therefore, the present invention is passed through
The method of offer can prepare the impact polypropylene material of high fondant-strength, high rigidity and high tenacity.It is this to possess premium properties
Polypropylene material be 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 each side, the different embodiments that the present invention records are (square
Case) each several part and the various features enumerated can be combined or all or part of exchange.In above-mentioned each embodiment
In, those suitably can be combined with reference to the embodiment of another embodiment with other embodiment, and this is by by this
Art personnel are to understand.In addition, it will be understood to those of skill in the art that description above is only the mode of example,
It is not intended to limit the present invention.
Claims (14)
1. a kind of high fondant-strength impact polypropylene material, including atactic copolymerized polypropene continuous phase and propylene-ethylene copolymers
Rubber domain, wherein the atactic copolymerized polypropene continuous phase is random altogether including at least the first atactic copolymerized polypropene and second
Poly- polypropylene, and first atactic copolymerized polypropene and the second atactic copolymerized polypropene are each independently selected from propylene-second
Olefinic random copolymer, propylene -1- butene random copolymers or ethylene-propylene -1- butene terpolymers；
The room temperature xylene soluble content of the material is more than or equal to 10 weight %, and is less than or equal to 35 weight %；And
And
The ratio between the Mw of the room temperature trichloro-benzenes DDGS of the material and the Mw of room temperature trichlorine benzene insoluble are more than 0.4, are less than or wait
In 1；
The atactic copolymerized polypropene continuous phase is with including the atactic copolymerized polypropene continuous phase and propylene-ethylene copolymers rubber
The ratio between melt index of polypropylene material of glue dispersed phase is more than or equal to 0.6, less than 1；
The material in the presence of the atactic copolymerized polypropene continuous phase and hydrogen by carrying out propylene-ethylene copolyreaction
The material comprising propylene-ethylene copolymers rubber domain is obtained to prepare.
2. material according to claim 1, it is characterised in that the ethene in the room temperature xylene soluble part of the material contains
Amount is more than or equal to 28 weight %, and is less than 45 weight %.
3. material according to claim 1, it is characterised in that the ethylene contents of the material are 8-20 weight %；And/or
Butene content is 0-10 weight %.
4. according to the material described in any one in claim 1-3, it is characterised in that the material at 230 DEG C, 2.16kg's
The melt index determined under load is 0.1-15g/10min.
5. according to the material described in any one in claim 1-3, it is characterised in that the material at 230 DEG C, 2.16kg's
The melt index determined under load is 0.1-6g/10min.
6. according to the material described in any one in claim 1-3, it is characterised in that the molecular weight distribution Mw/ of the material
Mn is less than or equal to 10, and more than or equal to 4；Mz+1/Mw is more than or equal to 10, and less than 20.
7. according to the material described in any one in claim 1-3, it is characterised in that first atactic copolymerized polypropene
Melt index is less than the melt index of second atactic copolymerized polypropene.
8. according to the material described in any one in claim 1-3, it is characterised in that first atactic copolymerized polypropene exists
230 DEG C, the melt index determined under 2.16kg load is 0.001-0.4g/10min；Including first random copolymerization poly- third
At 230 DEG C, the melt index determined under 2.16kg load is the atactic copolymerized polypropene of alkene and the second atactic copolymerized polypropene
0.1-15g/10min；And the weight ratio of first atactic copolymerized polypropene and the second atactic copolymerized polypropene is 40:60-
60:40。
9. material according to claim 8, it is characterised in that random including first atactic copolymerized polypropene and second
The melt index that the atactic copolymerized polypropene of COPP determines under 230 DEG C, 2.16kg load is 0.1-6g/10min.
10. according to the material described in any one in claim 1-3, it is characterised in that the atactic copolymerized polypropene has
Following feature：
Molecular weight distribution mw/mn=6-20；
The content that molecular weight is more than 5,000,000 fractions is more 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 more than or equal to 15.0 weight %, and is less than or equal to 40 weight %；
Mz+1/Mn is more than or equal to 70, and less than 150.
11. material according to claim 10, it is characterised in that the molecular weight distribution Mw/ of the atactic copolymerized polypropene
Mn=10-16.
12. according to the material described in any one in claim 1-3, it is characterised in that the atactic copolymerized polypropene is continuous
Ethylene contents are 0~6 weight % in phase；And/or 1- butene contents are 0~10 weight %.
13. according to the material described in any one in claim 1-3, it is characterised in that the material passes through random first
The copolyreaction of progress acrylic obtains random altogether comprising the first atactic copolymerized polypropene and second in the presence of COPP
Gather polyacrylic atactic copolymerized polypropene continuous phase, then carry out third in the presence of the atactic copolymerized polypropene continuous phase
Alkene-ethylene copolymer reacts to obtain the material comprising propylene-ethylene copolymers rubber domain to prepare.
14. according to the material described in any one in claim 1-3, it is characterised in that propylene-ethylene copolymers are total to random
The weight ratio of poly- polypropylene continuous phase is 11-80:100.
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| CN102933653A (en) * | 2010-06-10 | 2013-02-13 | 陶氏环球技术有限责任公司 | High stiffness high impact propylene impact copolymers field of the invention |
| CN103748163A (en) * | 2011-07-15 | 2014-04-23 | 博里利斯股份公司 | Unoriented film |
| CN103890081A (en) * | 2011-12-23 | 2014-06-25 | 博里利斯股份公司 | Process for the preparation of a heterophasic propylene copolymer |
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| CN102933653A (en) * | 2010-06-10 | 2013-02-13 | 陶氏环球技术有限责任公司 | High stiffness high impact propylene impact copolymers field of the invention |
| CN103748163A (en) * | 2011-07-15 | 2014-04-23 | 博里利斯股份公司 | Unoriented film |
| CN103890081A (en) * | 2011-12-23 | 2014-06-25 | 博里利斯股份公司 | Process for the preparation of a heterophasic propylene copolymer |
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